Name: 19790-60-4|3-(Benzyloxy)propanal|95%
Brand: Ambeed
SKU: A266125
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1
[ 50-00-0 ]
[ 6328-48-9 ]
[ 19790-60-4 ]

Yield	Reaction Conditions	Operation in experiment
	(i) H₂, Raney-Ni, semicarbazide, aq. EtOH, (ii) /BRN= 1209228/, H₂O; Multistep reaction;

Reference： [1]Gaiffe,A.; Launay,C. [Comptes Rendus des Seances de l'Academie des Sciences, Serie C: Sciences Chimiques, 1968, vol. 266, p. 1379 - 1380]

2
[ 4643-20-3 ]
[ 19790-60-4 ]
[ 140902-76-7 ]

Yield	Reaction Conditions	Operation in experiment
87%	With di-n-butylboryl trifluoromethanesulfonate; N-ethyl-N,N-diisopropylamine In dichloromethane at -78℃;
	With di-n-butylboryl trifluoromethanesulfonate; N-ethyl-N,N-diisopropylamine 1.) CH₂Cl₂, -78 to 0 deg C, 1.5 h, 2.) CH₂Cl₂, -78 deg C, 1.5 h; to 0 deg C; Yield given. Multistep reaction;

Reference： [1]Paterson, Ian; Smith, Julian D. [Journal of Organic Chemistry, 1992, vol. 57, # 12, p. 3261 - 3264]
[2]Paterson; Smith; Ward [Tetrahedron, 1995, vol. 51, # 34, p. 9413 - 9436]

3
[ 558-13-4 ]
[ 19790-60-4 ]
[ 119405-98-0 ]

Yield	Reaction Conditions	Operation in experiment
77%	With triphenylphosphine In dichloromethane at 0℃; for 1h;
	With triethylamine; triphenylphosphine In dichloromethane at -60℃; for 0.25h;
	Stage #1: carbon tetrabromide With triphenylphosphine In dichloromethane at 0℃; for 0.5h; Inert atmosphere; Stage #2: 3-Benzyloxypropanal In dichloromethane at 0 - 25℃; for 1.5h; Inert atmosphere;

Reference： [1]Harada, Toshiro; Katsuhira, Takeshi; Hara, Daiji; Kotani, Yasuo; Maejima, Keiji; et al. [Journal of Organic Chemistry, 1993, vol. 58, # 18, p. 4897 - 4907]
[2]Boden, Christopher D. J.; Pattenden, Gerald; Ye, Tao [Journal of the Chemical Society. Perkin transactions I, 1996, # 20, p. 2417 - 2419]
[3]Karmakar, Rajdip; Yun, Sang Young; Chen, Jiajia; Xia, Yuanzhi; Lee, Daesung [Angewandte Chemie - International Edition, 2015, vol. 54, # 22, p. 6582 - 6586][Angew. Chem., 2015, vol. 127, # 22, p. 6682 - 6686,5]

4
[ 4799-68-2 ]
[ 19790-60-4 ]

Yield	Reaction Conditions	Operation in experiment
97%	With Dess-Martin periodane; In dichloromethane; at 15℃; for 12h;Cooling with ice;	[0366] To a stirred solution of 3-benzyloxy-1 -propanol (5.0 g, 30.08 mmol) in dichloromethane (150 mE) was added Des s-Martin periodinane (19.13 g, 45.12 mmol) in an ice bath. The reaction mixture was stirred at 15 C. for 12 hours. The mixture was poured into saturated aqueous NaHCO3 solution (100 mE) and was extracted with dichloromethane (100 mEx2). The combined organic layers were dried over anhydrous Na2504, filtered and concentrated. The crude residue was purified by column chromatography (0-20% EtOAc in petroleum ether) to afford the title compound (4.8 g, yield 97%) as a light yellow oil. ?H NMR (400 MHz, CDC13) oe 9.80 (t, J=1.6 Hz, 1H), 7.37-7.29 (m, 5H), 4.53 (s, 2H), 3.82 (t, J=6.0 Hz, 2H), 2.72-2.68 (m, 2H).
95%	With silica gel; pyridinium chlorochromate; In dichloromethane; at 0 - 20℃; for 1h;	A solution of compound 10 (3.00 g, 18.07 mmol) inDCM (40 mL) was added slowly to a suspension of celite(6.00 g) in DCM (30 mL) at room temperature. To this suspensionpyridinium chlorochromate (PCC) (5.76 g, 26.76mmol) was added at 0 C and the reaction was kept at roomtemperature where the reaction was stirred for 1 h. Celite padfiltration followed by concentration of the filtrate provided aresidue that was purified by column chromatography (1:9).The purified aldehyde (2.82 g, 95%) was directly subjectedto allylation.Ti(OiPr)4 (0.65 g, 2.29 mmol) was added to a solution ofTiCl4 (0.14 g, 0.76 mmol) in DCM (15 mL) at 0 C under N2environment and the mixture was warmed to room temperatureand stirred for 1.5 h. Silver (I) oxide (0.35 g, 1.52mmol) was then added and the reaction was stirred for 6 hprohibiting direct light. Later DCM (40 mL) followed by (S)-BINOL (0.86 g, 3.05 mmol) were added to reaction mixtureat room temperature and the reaction was allowed to stir for2.5 h to give the chiral bis-Ti(IV) oxide (S, S)-1. The resultingcomplex was cooled to -15 oC to which aldehyde (2.50 g,15.24 mmol) followed by allyltributyltin (6.58 g, 19.81mmol) were added. The reaction was allowed to warm to 0oC and was further stirred for 15 h. The reaction wasquenched by adding saturated aqueous NaHCO3 (50 mL) andthe mixture was extracted with EtOAc (3 30 mL). Thecombined organic layer were separated and dried over anhydrousNa2SO4. Solvent was evaporated under reduced pressureand the crude product was purified by column chromatography (ethyl acetate / hexane, 1: 9) to afford pure (S)-1-(benzyloxy) hex-5-en-3-ol (8) (2.57 g, 82 %, ee 97%) as acolorless liquid. The optical rotation of the compound wasOOOi j OOO OOO3 : 6 (R)3a : 6 (S)4 : 6 (R)4a : 6 (S)1 : 6 (S)1a : 6 (R)Scheme 3. Synthesis of 3, 3a, 4 and 4a.Reagents, conditions and yields: i) CH3COCH=PPh3, C6H6, reflux, 10 h, 80 %, j) PhCH2CH2COCH=PPh3, C6H6, reflux, 14 h, 72 %.O OOBrOPPh3ref 18 g, h17Br+13 1416O15ref 18Scheme 4. Synthesis of 17.Reagents, conditions and yields: g) PPh3, benzene, reflux, 85% 24 h; h) 1 % NaOH, CH2Cl2, r.t., 1 h, 78%.320 Letters in Organic Chemistry, 2013, Vol. 10, No. 5 Shinde et al.[]D32 = - 2.6 (c = 1.0, CHCl3); IR: 3444, 1640, 1492, 1451,1363, 1207 cm-1; 1H NMR (CDCl3, 200 MHz): 7.38-7.22(5H, m), 5.79 (1H, m), 5.11-5.02 (2H, m), 4.50 (2H, s), 3.82(1H, m), 3.73-3.54 (2H, m), 2.71 (1H, brs), 2.21 (2H, t, J =7.0 Hz ), 1.77-1.66 (2H, m); 13C NMR (CDCl3, 50 MHz): 138.1, 135.0, 128.4, 127.9, 127.8, 118.0, 73.5, 70.5, 69.0,42.2, 36.0; ESIMS: m/z 229 [M+Na]+..
95%	With Dess-Martin periodane; In dichloromethane; at 0 - 20℃; for 3h;	To a solution of 3-(benzyioxy)propan-i-oi (7, 857 mg, 5 rnmoi) in dichioromethane(10 mL) was added Dess-Martin periodinane (2.4 g, 5.5 mmol) at 0 C( The reactionmixture was stirred at room temperature for 3 hours. Saturated aqueous sodium thiosulfate (10 mL) and saturated aqueous sodium bicarbonate (10 mE) were added, and the mixture was stirred for 30 minutes. The reaction mixture was filtered through celite and the phases separated. The organic layer was washed twice with brine, then concentrated to givecompound 8 as a colorless oil (780 mg), used without further purification.

88.2%	With oxalyl dichloride; dimethyl sulfoxide; triethylamine; In dichloromethane; at 20℃; for 1.5h;	Oxalyl chloride 35.0mL (52.1g, 414mmol) methylene 500mL chloride solution was cooled to -78 C of, dimethyl sulfoxide 38.5mL (42.4g, 542mmol) is added over a period of 18 minutes and the mixture was stirred for 25 minutes. Then, 3-benzyloxy-1-ol 43.0mL (45.1g, 271mmol) was added and stirred over a period of 20 minutes to 70 minutes. Further, after stirring triethylamine 151mL (110g, 1090mmol) over a period of 5 minutes plus 10 minutes, and stirred for 1.5 hours then warmed to room temperature. It was then extracted with methylene chloride by the addition of 0.5N hydrochloric acid aqueous solution of 400mL (200mmol). Twice and the organic layer with 0.5N aqueous hydrochloric acid, once with saturated brine, and dried over anhydrous sodium sulfate. The residue obtained and the solvent evaporated silica gel column chromatography (Biotage, elution solvent; hexane / ethyl acetate = 97 / 3-60 / 40) to obtain the title compound 39.3g (yield 88.2 %) was obtained as an oil. H-NMR (CDCl 3) delta: 9.81 (1H, t, J = 1.8 Hz), 7.43-7.27 (5H, m), 4.54 (2H, s), 3.82 (2H, t, J = 6.1 Hz ), 2.71 (2H, td, J = 6.1, 1.8 Hz).
84%	With Dess-Martin periodane; In dichloromethane; at 20℃; for 0.5h;	Steps 1 and 2: To 3-benzoxypropanol (168 mg, 1 mmol) in 20 ml DCM was added Dess Martin reagent (636 mg, 1.5 mmol) and was stirred at rt for 0.5 h. The reaction mixture was filtered and the filtrate was directly placed on top of a column and was eluted with hexane and EtOAc to afford colorless oil (139 mg, 84%). The resulting aldehyde was dissolved in DCE (10 mL) and 3-(4-amino-1-oxoisoindolin-2- yl)piperidine-2,6-dione (130 mg, 0.5 mmol), AcOH (60 mg, 1 mmol) were added. The mixture was stirred at rt for 2 h. Sodium triacetoxyborohydride (159 mg, 0.75 mmol) was added and stirred for additional 18 h. Directly placed the reaction mixture on top of a silica column and eluted with DCM and MeOH to provide a white solid (140 mg, 69%). ESI-MS :408.25.
81%	With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione; In dimethyl sulfoxide; at 20℃; for 17h;Cooling with ice;	Step 1: (S)-Benzyl 4-methyl-2-(phenylmethylsulfonamido)pentanoate (0472) To a solution of 3-(benzyloxy) propan-1-ol (10.0 g, 60.24 mmol) in DMSO (100 mL) was added IBX (20.2 g, 72.29 mmol) under ice-bath. The mixture was warmed to room temperature and stirred at this temperature for 17 hrs. The reaction mixture was poured into water (300 mL) and extracted with EA (200 mL×2), the organic phase was washed with water (200 mL×3), and brine (100 mL), dried (Na2SO4), and the solution was concentrated and the crude was purified by SGC to obtain a light yellow liquid. (8.0 g, 81%). (0473) 1H NMR (500 MHz, CDCl3) delta 9.77 (s, 1H), 7.36-7.26 (m, 5H), 4.53 (s, 2H), 3.8-3.83 (m, 2H), 2.71-2.68 (m, 2H).
79%	With PCC; In dichloromethane;	3-(Benzyloxy)propanal To a suspension of PCC (606 mg, 2.82 mmol) in anhydrous dichloromethane (8 mL) at room temperature under N2 was added a solution of 3-benzyloxy-1-propanol (310 mg, 1.88 mmol) in anhydrous dichloromethane. The reaction mixture was stirred overnight at room temperature, filtrated through Celite, and concentrated. The residue was purified by column chromatography on silica gel (1-10% ethyl acetate/hexanes) to give 3-(benzyloxy)propanal (243 mg, 79%).
79%	With pyridinium chlorochromate; In dichloromethane; at 20℃;	To a suspension of PCC (606 mg, 2.82 mmol) in anhydrous dichloromethane (8 mL) at room temperature under N2 was added a solution of 3-benzyloxy-1-propanol (310 mg, 1.88 mmol) in anhydrous dichloromethane. The reaction mixture was stirred overnight at room temperature, filtrated through Celite, and concentrated. The residue was purified by column chromatography on silica gel (1-10% ethyl acetate/hexanes) to give 3-(benzyloxy)propanal (243 mg, 79%).
77%		Dimethyl sufoxide (1.1 ml, 16 mmol) was added to a solution of oxalyl chloride (0.7 ml, 8 mmol) in DCM (100 ml) at -78 C. The reaction mixture was stirred for 10 min after which time <strong>[4799-68-2]3-benzyloxypropan-1-ol</strong> (370, 1.20 g, 1 equiv) in DCM (5 ml) was added dropwise. After 15 min, triethylamine (5.1 ml, 36 mmol) was added, the solution stirred for 5 min, and then the reaction mixture warmed to room temperature. After stirring for 30 min the reaction was quenched with saturated ammonium chloride solution (15 ml), and the aqueous phase was washed with DCM (2×40 ml). The combined organic phase was washed with saturated NaHCO3 (2×20 ml), brine (20 ml), dried (MgSO4) and concentrated. Purification by flash chromatography (petrol/diethyl ether=2:1) gave the title compound as a clear oil (0.91 g, 77%); Rf 0.35 (petrol/diethyl ether 2:1); numax/cm-1 (neat) 3032 [Ar(C-H)], 1726 (CO), 1495, 1444, 1362, 1209, 1101, 906, 737, 691; deltaH (300 MHz, CDCl3) 9.82 (1H, s, CHO), 7.28-7.41 (5H, m, Ar-H), 4.55 (2H, s, PhCH2O), 3.84 (2H, t, J=6.1 Hz, CH2OCH2Ph), 2.72 (2H, t, J=6.1 Hz, OCH2CH2CHO); deltaC (75 MHz, CDCl3) 200.9 (CHO), 137.6 (Cipso), 128.2 [2× C(Ar)], 127.5 [2× C(Ar)], 127.4 (C(Ar)), 72.9, 63.5 and 43.6 (3× CH2); m/z (CI) 165 [(MH)+, 100%], 147 [(MH)+-H2O, 40], 107 [(MH)+-C3H8O, 95].
75%	With oxalyl dichloride; dimethyl sulfoxide; triethylamine; In dichloromethane; at -78℃; for 1.33333h;	[0295] Step A: (J. Org. Chem. 53:911 (1988)) [0296] To a solution of oxalyl chloride (5.7 mL, 97 mmol) in dichloromethane (200 mL) at -78 C. was added dimethyl sulfoxide (9.2 mL, 130 mmol). The reaction mixture was stirred at -78 C. for 20 min before addition of 3-(benzyloxy)propan-1-ol (11 g, 65 mmol) in dichloromethane (25 mL). After an hour at -78 C., reaction was quenched with triethylamine (19 mL, 260 mmol) and warmed to room temperature. Work-up and column chromatography by elution with dichloromethane resulted in 8 g (75%) of 3-(benzyloxy)propan-1-al. [0297] Step B: [0298] To a solution of 3-(benzyloxy)propan-1-al (1 g, 6.1 mmol) in THF at 0 C. was added a 1M solution of 4-fluorophenylmagnesium bromide in THF (6.7 mL, 6.7 mmol). The reaction was warmed to room temperature and stirred for 1 h. Work-up and column chromatography by elution with dichloromethane resulted in 0.7 g (44%) of alcohol. [0299] Step C: [0300] To a solution of benzyl ether (500 mg) in ethyl acetate (10 mL) was added 10% Pd(OH)2-C (100 mg). The reaction was stirred under hydrogen gas for 16 h. The reaction mixture was filtered through celite and concentrated. Chromatography of the residue by elution with ethyl acetate-dichloromethane (1:1) resulted in 340 mg (79%) of product.
71.3%	With Dess-Martin periodane; In dichloromethane; for 2h;Inert atmosphere;	Add Dess-Martin oxidant to a 250 mL flask(14.33 g, 33.79 mmol), argon-protected, 40 mL dichloromethane.30 mL of a solution of Compound C (4.68 g, 28.16 mmol) in dichloromethane was added dropwise.Stir for 2 h. Add 20 mL of saturated sodium thiosulfate solution,Add 40 mL of saturated sodium bicarbonate solution to quench the reaction.Extract three times with dichloromethane, combine the organic phases, and dry.The solvent was dried and the PE:EA gradient eluted through the column.3.30g of compound D (colorless liquid)The yield was 71.3%.
70%		To a solution of DMSO (14.1 g, 180.5 mmol,3.0 equiv.) in dry DCM (100 mL) at -78 oC, a solution of oxalylchloride (7.7 mL, 90.2 mmol, 1.5 equiv.) in DCM (50 mL) was added dropwiseunder nitrogen atmosphere. After 1h, a solution of 3-(benzyloxy)propanol (10 g,60.1 mmol, 1 equiv.) in DCM (70 mL) was added at the same temperature andstirred for 3h. To this, triethylamine (33.5 mL, 240.6 mmol, 4 equiv.) wasadded at the same temperature and then further stirred at 0 oC foranother 3h. After completion of the reaction, the reaction mixture was quenchedwith water. The organic layer was washed with water and brine, dried overanhydrous sodium sulfate, concentrated under reduced pressure to afford thecrude product which was further purified by column chromatography usingpetroleum ether/EtOAc (9:1) as eluent to afford the desired product.Colourlessliquid; Yield 70% (7.0 g); 1H NMR (400 MHz, CDCl3): delta2.68-2.72 (m, 2H), 3.81 (t, J = 6.1Hz, 2H), 4.53 (s, 2H), 7.31-7.35 (m, 5H), 9.80 (t, J = 1.8 Hz, 1H); 13CNMR (100 MHz, CDCl3): delta 43.9, 63.8, 73.3, 127.7, 127.8, 128.5,137.9, 201.2; HRMS (ESI-TOF) m/z: calc?dfor C10H12O2 ([M+Na]+): 187.0730;found 187.0730.
40%		Compound 227.1. 3-(Benzyloxy)propanal. Into a 100-mL three neck round-bottom flask, which was purged and maintained with an inert atmosphere of nitrogen, was placed DMSO (5.1 mL, 71.79 mmol) in dichloromethane (40 mL). This was followed by the addition of oxalyl chloride (3.1 mL, 54.16 mmol) dropwise at -78 C and stirred for 30 min at -78 C. To this was added a solution of 3-(benzyloxy)propan-l-ol (4.8 niL, 30.08 mmol) in dichloromethane (10 niL) dropwise at -78 C. The resulting solution was stirred for 1 h at -78 C, then triethylamine (16.5 mL, 118.59 mmol) was added to the reaction. The resulting solution was stirred for 1 h at -78 to -20 C, then quenched with 50 mL of NH4C1 (sat.). The aqueous phase was extracted with 2 x 50 mL of dichloromethane. The combined organic layers were dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography with EtOAc:PE (1 :5) as eluent to furnish title compound as light yellow oil.
		Example 3; Preparation of 1-(Aryl)-Propane-1,3-Diol from Propane-1,3-Diol Via Grignard Addition; Step A: (J. Org. Chem. 53:911 (1988)) To a solution of oxalyl chloride (5.7 mL, 97 mmol) in dichloromethane (200 mL) at -78 C. was added dimethyl sulfoxide (9.2 mL, 130 mmol). The reaction mixture was stirred at -78 C. for 20 min before addition of 3-(benzyloxy)propan-1-ol (11 g, 65 mmol) in dichloromethane (25 mL). After an hour at -78 C., reaction was quenched with triethylamine (19 mL, 260 mmol) and warmed to room temperature. Work-up and column chromatography by elution with dichloromethane resulted in 8 g of 3-(benzyloxy)propan-1-al.
		To a solution of oxalyl chloride (5.7 mL, 97 mmol) in dichloromethane (200 mL) at -780C was added dimethyl sulfoxide (9.2 mL, 130 mmol). The reaction mixture was stirred at-78 C for 20 min before addition of 3-(benzyloxy)propan-l-ol (11 g, 65 mmol) in dichloromethane (25 mL). After an hour at -78 "C5 reaction was quenched with triethylamine (19 mL, 260 mmol) and warmed to room temperature. Work-up and column chromatography by elution with dichloromethane resulted in 8 g of 3-(benzyloxy)propan-1-al.

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[103]Synlett,2011,p. 2719 - 2724
[104]European Journal of Organic Chemistry,2012,p. 398 - 408
[105]Angewandte Chemie - International Edition,2012,vol. 51,p. 2972 - 2976
[106]Bioorganic and Medicinal Chemistry Letters,2012,vol. 22,p. 2415 - 2417
[107]Chemistry - A European Journal,2012,vol. 18,p. 16823 - 16827
[108]Helvetica Chimica Acta,2013,vol. 96,p. 1948 - 1954
[109]Organic Process Research and Development,2013,vol. 17,p. 1247 - 1251
[110]Tetrahedron Letters,2014,vol. 55,p. 4189 - 4192
[111]Patent: US2014/228219,2014,A1 .Location in patent: Paragraph 0767-0768
[112]Molecular Crystals and Liquid Crystals,2014,vol. 593,p. 61 - 77
[113]Organic and Biomolecular Chemistry,2015,vol. 13,p. 2546 - 2549
[114]Patent: US2015/175650,2015,A1 .Location in patent: Paragraph 0083; 0176
[115]Tetrahedron Letters,2011,vol. 52,p. 1788 - 1790
[116]Patent: US2015/289505,2015,A1 .Location in patent: Paragraph 0898-0900
[117]Patent: WO2016/44559,2016,A1 .Location in patent: Page/Page column 38; 53; 54
[118]Journal of Organic Chemistry,2016,vol. 81,p. 2189 - 2193
[119]Synthesis,2016,vol. 48,p. 1181 - 1190
[120]Patent: WO2016/154081,2016,A1 .Location in patent: Page/Page column 48
[121]ChemPlusChem,2016,vol. 81,p. 1160 - 1165
[122]Patent: WO2016/209847,2016,A1 .Location in patent: Page/Page column 64; 65
[123]Organic Letters,2017,vol. 19,p. 834 - 837
[124]Synlett,2017,vol. 28,p. 583 - 588
[125]Patent: WO2018/200625,2018,A1 .Location in patent: Paragraph 00353; 00354; 00355
[126]Journal of the American Chemical Society,2020,vol. 142,p. 726 - 732

5
[ 6328-48-9 ]
[ 19790-60-4 ]

Yield	Reaction Conditions	Operation in experiment
78%	With diisobutylaluminium hydride In hexane; toluene at 0℃; for 2h; Inert atmosphere;
	With diisobutylaluminium hydride In tetrahydrofuran; hexane at 23℃; for 1h; Yield given;
1.10 g	With diisobutylaluminium hydride In tetrahydrofuran; hexane; toluene for 2h; Ambient temperature;

Reference： [1]Vintonyak, Viktor V.; Maier, Martin E. [Organic Letters, 2008, vol. 10, # 6, p. 1239 - 1242]
[2]Overman,L.E.; Bell,K.L.; Ito,F. [Journal of the American Chemical Society, 1984, vol. 106, p. 4192]
[3]Ohtsuka; Fushihara; Kobayashi; Kawamura; Iimori; Oishi [Chemical and Pharmaceutical Bulletin, 1992, vol. 40, # 3, p. 617 - 623]

6
[ 19790-60-4 ]
[ 1826-67-1 ]
[ 117661-29-7 ]

Yield	Reaction Conditions	Operation in experiment
83%	In tetrahydrofuran at -20℃; for 3h; Inert atmosphere;
80%	Stage #1: 3-Benzyloxypropanal; vinyl magnesium bromide With copper(l) cyanide In tetrahydrofuran at 0 - 40℃; Stage #2: With water; ammonium chloride In tetrahydrofuran
80%	In tetrahydrofuran at 0 - 20℃; for 9h; Inert atmosphere;

69%	In tetrahydrofuran at 0℃; for 2h;
	With cerium(III) chloride 1) THF, -78 deg C, 1 h, 2a) THF, -78 deg C, 4 h, b) -65 deg C, 2 h; Yield given. Multistep reaction;
	In tetrahydrofuran at 0 - 20℃; Inert atmosphere;
	In tetrahydrofuran at 0℃; for 1h; Inert atmosphere;	Preparation of Compound 2 (Scheme 11a) Propylene glycol (500 g) was combined with benzyl bromide (100 g, 1.0 eq.) under nitrogen. Sodium hydroxide (28 g, 1.2 eq.) was added and the mixture was stirred at 20 deg C. for 4 hours. Ethyl acetate (800 mL) was then added and the mixture was washed with water (500 mL). The organic phase was dried over anhydrous sodium sulfate, filtered and concentrated to dryness giving the desired crude 3-benzyloxypropanol (100 g) as a yellow oil. 1H NMR (300 MHz, CDCl3): δ 1.85-1.90 (m, 2H), 3.65 (t, 2H), 3.80 (t, 2H), 4.25 (t, 1H), 4.55 (s, 2H), 7.25-7.40 (m, 5H). Crude 3-benzyloxypropanol (100 g, 1.0 eq.) was combined with dimethyl sulfoxide (DMSO, 500 mL) and tetrahydrofuran (THF, 500 mL) under nitrogen. 2-lodoxybenzoic acid (IBX, 253 g, 1.5 eq.) was added and the reaction was stirred at 20 deg C. for 12 hours. Ethyl acetate (1500 mL) was then added and the mixture was washed with saturated aqueous sodium sulfite (500 mL) and saturated aqueous sodium bicarbonate (500 mL). The organic phase was washed with anhydrous sodium sulfate, filtered and concentrated to dryness. The residue was purified on silica gel (ethyl acetate/hexane 1/20) giving the desired 3-benzyloxypropionaldehyde (30 g) as a yellow oil. 1H NMR (300 MHz, CDCl3): δ 2.70 (m, 2H), 3.80 (t, 2H), 4.55 (s, 2H), 7.25-7.40 (m, 5H), 9.80 (s, 1H). 3-benzyloxypropionaldehyde (30 g, 1.0 eq.) was dissolved in THF under nitrogen and cooled to 0 deg C. Vinylmagnesium bromide (1M, 220 mL, 1.2 eq.) was added and the reaction was stirred at 0 deg C. for 1 hour. Saturated aqueous ammonium chloride (100 mL) was then added and the mixture was extracted with dichloromethane (DCM, 3×100 mL). The organic extracts were dried over anhydrous sodium sulfate, filtered and concentrated to dryness giving crude 5-benzyloxy-pent-1-ene-3-ol. 1H NMR (300 MHz, CDCl3): δ 1.75-1.99 (m, 2H), 3.60-3.75 (m, 2H), 4.30-4.40 (m, 1H), 4.50 (s, 2H), 4.70 (s, 1H), 5.10-5.15 (m, 1H), 5.25-5.30 (m, 1H), 5.80-5.95 (m, 1H), 7.25-7.40 (m, 5H). This material was dissolved in DMSO (120 mL) and THF (120 mL) under nitrogen and IBX (65 g, 1.5 eq.) was added. The mixture was stirred at 20 deg C. for 12 hours after which, ethyl acetate (500 mL) was added. The resulting mixture was washed with saturated aqueous sodium sulfite (200 mL) and saturated aqueous sodium bicarbonate (200 mL). The organic phase was dried over anhydrous sodium sulfate, filtered and concentrated to dryness. The residue was purified on silica gel (ethyl acetate/hexane 1/20) giving the desired 5-benzyloxy-pent-1-ene-3-one (12.7 g) as a yellow oil. 1H NMR (300 MHz, CDCl3): δ 2.95 (t, 2H), 3.80 (t, 2H), 4.55 (s, 3H), 5.85 (d, 1H), 6.20-6.40 (m, 2H), 7.20-7.40 (m, 5H).
	In tetrahydrofuran at 0℃; for 1h; Inert atmosphere;	17 Propylene glycol (500 g) is combined with benzyl bromide (100 g, 1.0 eq.) under nitrogen. Sodium hydroxide (28 g, 1.2 eq.) is added and the mixture is stirred at 20 deg C for 4 hours. Ethyl acetate (800 mL) is then added and the mixture is washed with water (500 mL). The organic phase is dried over anhydrous sodium sulfate, is filtered and is concentrated to dryness giving the desired crude 3-benzyloxypropanol (100 g) as a yellow oil. 1H NMR (300 MHz, CDCI3): 6 1.85-1.90 (m, 2H), 3.65 (t, 2H), 3.80 (t, 2H), 4.25 (t, 1H), 4.55 (s, 2H), 7.25- 7.40 (m, 5H). Crude 3-benzyloxypropanol (100 g, 1.0 eq.) is combined with dimethyl sulfoxide (DMSO, 500 mL) and tetrahydrofuran (THF, 500 mL) under nitrogen. 2-lodoxybenzoic acid (IBX, 253 g, 1.5 eq.) is added and the reaction is stirred at 20 deg C for 12 hours. Ethyl acetate (1500 mL) is then added and the mixture is washed with saturated aqueous sodium sulfite (500 mL) and saturated aqueous sodium bicarbonate (500 mL). The organic phase is washed with anhydrous sodium sulfate, is filtered and is concentrated to dryness. The residue is purified on silica gel (ethyl acetate/hexane 1/20) giving the desired 3-benzyloxypropionaldehyde (30 g) as a yellow oil. 1H NMR (300 MHz, CDCI3): 6 2.70 (m, 2H), 3.80 (t, 2H), 4.55 (s, 2H), 7.25-7.40 (m, 5H), 9.80 (s, 1H). 3-benzyloxypropionaldehyde (30 g, 1.0 eq.) is dissolved in THF under nitrogen and is cooled to 0 deg C. Vinylmagnesium bromide(lM, 220 mL, 1.2 eq.) is added and the reaction is stirred at 0 deg C for 1 hour. Saturated aqueous ammonium chloride (100 mL) is then added and the mixture is extracted with dichloromethane (DCM, 3 x 100 mL). The organic extracts are dried over anhydrous sodium sulfate, are filtered and are concentrated to dryness giving crude 5-benzyloxy-pent-l-ene-3-ol. 1H NMR (300 MHz, CDCI3): 6 1.75-1.99 (m, 2H), 3.60-3.75 (m, 2H), 4.30-4.40 (m, 1H), 4.50 (s, 2H), 4.70 (s, 1H), 5.10-5.15 (m, 1H), 5.25-5.30 (m, 1H), 5.80-5.95 (m, 1H), 7.25-7.40 (m, 5H). This material is dissolved in DMSO (120 mL) and THF (120 mL) under nitrogen and IBX (65 g, 1.5 eq.) is added. The mixture is stirred at 20 deg C for 12 hours after which, ethyl acetate (500 mL) is added. The resulting mixture is washed with saturated aqueous sodium sulfite (200 mL) and saturated aqueous sodium bicarbonate (200 mL). The organic phase is dried over anhydrous sodium sulfate, is filtered and is concentrated to dryness. The residue is purified on silica gel (ethyl acetate/hexane 1/20) giving the desired 5- benzyloxy-pent-l-ene-3-one (12.7 g) as a yellow oil. 1H NMR (300 MHz, CDCI3): 6 2.95 (t, 2H), 3.80 (t, 2H), 4.55 (s, 3H), 5.85 (d, 1H), 6.20-6.40 (m, 2H), 7.20-7.40 (m, 5H).
0.85 g	In tetrahydrofuran at 0 - 20℃; for 6h; Inert atmosphere;	5-(Benzyloxy)pent-1-en-3-ol (26); Typical Procedure Dess-Martin periodinane (2.6 g, 6.0 mmol) was added portionwise to a stirred solution of 3-(benzyloxy)propan-1-ol (24, 1 g, 6.0 mmol) in anhyd CH2Cl2 (20 mL), at 0 °C under a N2 atmosphere and stirring was continued for 2 h at r.t. The mixture was then diluted with CH2Cl2 (50mL) and quenched with sat. aq Na2S2O3 and sat. aq NaHCO3 mixture(1:1, 20 mL). The organic part was then successively washed with H2O(50 mL) and brine (50 mL), and dried (anhyd MgSO4). It was then filteredand the filtrate was concentrated in vacuo to leave the crude aldehyde(920 mg), which was used directly in the next step. The crude aldehyde was dissolved in anhyd THF (15 mL) and cooled to 0 °C undera N2 atmosphere. Vinylmagnesium bromide (2 M in THF, 4.0 mL, 8mmol) was then added dropwise to the solution of the aldehyde and the mixture was stirred for 30 min at 0 °C; it was then allowed tocome to r.t. and stirred for 5 h. The mixture was cooled to 0 °C andthen quenched by dropwise addition of sat. aq NH4Cl (5 mL). The volatiles were removed under reduced pressure and the residue was diluted with CH2Cl2 (80 mL). The organic solution was washed successively with 10% aq NH4Cl solution (2 × 50 mL), H2O (100 mL), andbrine (100 mL), and then dried (anhyd MgSO4) and filtered. The filtrate was concentrated under reduced pressure to provide the crude allylic alcohol which on column chromatography (silica gel, EtOAc-PE, 1:9) provided the allylic alcohol as a colorless liquid; yield: 0.850 g(74%).IR (CHCl3): 3428, 2936, 1642, 1450, 1103, 928 cm-1.1H NMR (400 MHz, CDCl3): δ = 7.31-7.14 (m, 5 H), 5.82-5.73 (m, 1 H),5.17 (d, J = 17.2 Hz, 1 H), 5.01 (d, J = 10.4 Hz, 1 H), 4.42 (s, 2 H), 4.26-4.22 (m, 1 H), 3.63-3.58 (m, 1 H), 3.55-3.51 (m, 1 H), 3.29 (br s, 1 H),1.81-1.68 (m, 2 H).13C NMR (100 MHz, CDCl3): δ = 140.6, 138.0, 128.5, 127.8, 127.7,114.4, 73.3, 71.7, 68.3, 36.4.HRMS: m/z [M + Na]+ calcd for C12H16NaO2: 215.1048; found:215.1029.
	In tetrahydrofuran at 0℃; for 1h; Inert atmosphere;	17 EXAMPLE 17 - Preparation of compound 2 (Scheme 11a) Propylene glycol (500 g) is combined with benzyl bromide (100 g, 1.0 eq.) under nitrogen. Sodium hydroxide (28 g, 1.2 eq.) is added and the mixture is stirred at 20 deg C for 4 hours. Ethyl acetate (800 mL) is then added and the mixture is washed with water (500 mL). The organic phase is dried over anhydrous sodium sulfate, is filtered and is concentrated to dryness giving the desired crude 3-benzyloxypropanol (100 g) as a yellow oil. 1H NMR (300 MHz, CDCI3): 61.85-1.90 (m, 2H), 3.65 (t, 2H), 3.80 (t, 2H), 4.25 (t, 1H), 4.55 (s, 2H), 7.25-7.40 (m, 5H). Crude 3-benzyloxypropanol (100 g, 1.0 eq.) is combined with dimethyl sulfoxide (DMSO, 500 mL) and tetrahydrofuran (THF, 500 mL) under nitrogen. 2-lodoxybenzoic acid (IBX, 253 g, 1.5 eq.) is added and the reaction is stirred at 20 deg C for 12 hours. Ethyl acetate (1500 mL) is then added and the mixture is washed with saturated aqueous sodium sulfite (500 mL) and saturated aqueous sodium bicarbonate (500 mL). The organic phase is washed with anhydrous sodium sulfate, is filtered and is concentrated to dryness. The residue is purified on silica gel (ethyl acetate/hexane 1/20) giving the desired 3-benzyloxypropionaldehyde (30 g) as a yellow oil. 1H NMR (300 MHz, CDCI3): 62.70 (m, 2H), 3.80 (t, 2H), 4.55 (s, 2H), 7.25-7.40 (m, 5H), 9.80 (s, 1H). 3-benzyloxypropionaldehyde (30 g, 1.0 eq.) is dissolved in THF under nitrogen and is cooled to 0 deg C. Vinylmagnesium bromide(1M, 220 mL, 1.2 eq.) is added and the reaction is stirred at 0 deg C for 1 hour. Saturated aqueous ammonium chloride (100 mL) is then added and the mixture is extracted with dichloromethane (DCM, 3 x 100 mL). The organic extracts are dried over anhydrous sodium sulfate, are filtered and are concentrated to dryness giving crude 5- benzyloxy-pent-1-ene-3-ol. 1H NMR (300 MHz, CDCI3): 61.75-1.99 (m, 2H), 3.60-3.75 (m, 2H), 4.30-4.40 (m, 1H), 4.50 (s, 2H), 4.70 (s, 1H), 5.10-5.15 (m, 1H), 5.25-5.30 (m, 1H), 5.80- 5.95 (m, 1H), 7.25-7.40 (m, 5H). This material is dissolved in DMSO (120 mL) and THF (120 mL) under nitrogen and IBX (65 g, 1.5 eq.) is added. The mixture is stirred at 20 deg C for 12 hours after which, ethyl acetate (500 mL) is added. The resulting mixture is washed with saturated aqueous sodium sulfite (200 mL) and saturated aqueous sodium bicarbonate (200 mL). The organic phase is dried over anhydrous sodium sulfate, is filtered and is concentrated to dryness. The residue is purified on silica gel (ethyl acetate/hexane 1/20) giving the desired 5- benzyloxy-pent-1-ene-3-one (12.7 g) as a yellow oil. 1H NMR (300 MHz, CDCI3): 62.95 (t, 2H), 3.80 (t, 2H), 4.55 (s, 3H), 5.85 (d, 1H), 6.20-6.40 (m, 2H), 7.20-7.40 (m, 5H).
	In tetrahydrofuran; diethyl ether at 0 - 20℃; for 0.408333h; Inert atmosphere;
	In tetrahydrofuran at 0 - 20℃; for 1h; Inert atmosphere;

Reference： [1]Location in patent: experimental part Oh, Chang Hyun; Yoo, Kyung Ho; Hong, Joon Hee [Bulletin of the Korean Chemical Society, 2010, vol. 31, # 9, p. 2473 - 2478]
[2]Location in patent: experimental part Yadav; Anantha Lakshmi; Mallikarjuna Reddy; Prasad, Attaluri R.; Subba Reddy, Basi V. [Tetrahedron, 2010, vol. 66, # 1, p. 334 - 338]
[3]Gontala, Arjun; Woo, Sang Kook [Advanced Synthesis and Catalysis, 2020, vol. 362, # 15, p. 3223 - 3228]
[4]Matsumoto, Kazutsugu; Fuwa, Seiji; Shimojo, Megumi; Kitajima, Hidehiko [Bulletin of the Chemical Society of Japan, 1996, vol. 69, # 10, p. 2977 - 2987]
[5]Holmes, Andrew B.; Hughes, Andrew B.; Smith, Adrian L.; Williams, Simon F. [Journal of the Chemical Society. Perkin transactions I, 1992, # 9, p. 1089 - 1100]
[6]Zhang, Ping; Brozek, Laura A.; Morken, James P. [Journal of the American Chemical Society, 2010, vol. 132, # 31, p. 10686 - 10688]
[7]Current Patent Assignee: PREVACUS INC - US2015/175650, 2015, A1 Location in patent: Paragraph 0083; 0176
[8]Current Patent Assignee: PREVACUS INC - WO2016/44559, 2016, A1 Location in patent: Page/Page column 38; 53; 54
[9]Mukherjee, Jyoti Prasad; Sil, Suman; Pahari, Amit K.; Chattopadhyay, Shital K. [Synthesis, 2016, vol. 48, # 8, p. 1181 - 1190]
[10]Current Patent Assignee: PREVACUS INC - WO2016/209847, 2016, A1 Location in patent: Page/Page column 64; 65
[11]Knowles, Robert R.; Metrano, Anthony J.; Tsuchiya, Yuto; Tsui, Elaine [Angewandte Chemie - International Edition, 2020, vol. 59, # 29, p. 11845 - 11849][Angew. Chem.]
[12]Jung, Woo-Ok; Yoo, Minjin; Migliozzi, Madyson M.; Zbieg, Jason R.; Stivala, Craig E.; Krische, Michael J. [Organic Letters, 2022, vol. 24, # 1, p. 441 - 445]

7
[ 107-02-8 ]
[ 100-51-6 ]
[ 19790-60-4 ]

Yield	Reaction Conditions	Operation in experiment
31%	With sodium hydroxide; acetic acid; chloroacetic acid In water at 40℃; for 80h;
	Stage #1: acrolein; benzyl alcohol With chloroacetic acid; sodium hydroxide In water for 0.25h; Stage #2: With acetic acid In water at 40℃; for 80h;	3-Benzyloxypropionaldehyde (2a) In a mixture of phenyl methanol (61.5 mL, 64.25 g, 0.595 mol), 2-chloroethanoic acid (3.36 g), and NaOH (1.425 g) in 7.50 mL water added slowly with gentle shaking for 15 min to acroleine (50 mL, 42.95 g, 0.75 mol). At 40 °C 15 mL aceteic acid drop wise added to the reaction system and maintained it at 40 °C during 80 hours. The crude reaction mixture was worked up with EtOAc and acid was removed by wash with aqua (75 mL x 3) and passed through anhydrous MgSO4. After work up the organic solvent was dried and crude product made pure by vacuum distillation at 100 °C (0.3 mm Hg) pressure followed by the removal of volatile starting materials and side products. The residue remained as viscous oil was aldehyde 2a confirmed from NMR studies. The raw material was taken for subsequent steps and there is no necessary for purication. Crude yield was 33 g (32%). Proton NMR values were determined by deuterium chloroform; Proton-NMR δ: 9.78 (-CHO), 7.29 (Ar-H), 4.52 (C6H5CH2), 3.80 (-O-CH2), 2.68 (-CH2); C-13 NMR (CDCl3) δ : 200.87, 137.70, 127.50 and 127.34 (aromatic), 72.92 (benzylic), 66.57, 43.58; MS (C9H10O2) calcd. 150.068 found MH+ 151.1.

Reference： [1]Wang, Yuqiang; Farquhar, David [Journal of Medicinal Chemistry, 1991, vol. 34, # 1, p. 197 - 203]
[2]Pal, Ashutosh [Oriental Journal of Chemistry, 2021, vol. 37, # 2, p. 295 - 301]

8
[ 19790-60-4 ]
[ 1099-45-2 ]
[ 70542-83-5 ]

Yield	Reaction Conditions	Operation in experiment
68%	In dichloromethane
	In benzene
	In dichloromethane at 20℃; for 36h;

28 g	In dichloromethane at 20℃;
6.15 g	In benzene at 20℃; for 3h; Inert atmosphere;
65 g	In dichloromethane at 20℃; for 8h;	(E)-Ethyl 5-(benzyloxy)pent-2-enoate (III) 3-(benzyloxy)propan-1-ol6 (83g, 0.5 mol) was mixed with was dissolved in CH2Cl2 (800 mL) and the pyridinium chlorochromate (on Al2O3, 1mM/1g, 700 g, 0.7 mol) was added.The mixture was stirred for 1 hour and filtered; the precipitate was washed by ethyl acetate (300 mL). The solvents were evaporated yielding crude 3-(benzyloxy)propanal, which was then purified by flash chromatography (EtOAc:hexane 1:3) to allow yellowish liquid that was used in next step without further purification. 3-(benzyloxy)propanal from previous stage (65 g, appr 0.4 mol) was dissolved in dry CH2Cl2(400 mL). The solution of ethyl 2-(triphenylphosphoranylidene)acetate 7 (140g, 0.4 mol) in dry CH2Cl2 (300 mL) was added and the mixture was stirred at the room temperature for 8 hours. The solvent was evaporated and the product was purified by column chromatography (EtOAc:hexane 1:4): colorless liquid III (65 g, 56% two steps). 1H NMR (700 MHz, CDCl3, 300K): δ = 7.37-7.33 (m, 3H), 7.30 (t, J = 4 Hz, 1H), 6.99 (dt, J =15.6 Hz, 6.9 Hz, 1H), 6.99 (dt, J = 15.6 Hz, 1.3 Hz, 1H), 4.53 (s, 2H), 4.21 (q, J = 7.2 Hz, 2H),3.60 (t, J = 6.5 Hz, 2H), 2.53 (ddd, J = 6.9 Hz, 6.5 Hz, 1.3 Hz, 2H), 1.30 (t, J = 7.2 Hz, 3H).

Reference： [1]Location in patent: scheme or table Pattenden, Gerald; Ashweek, Neil J.; Baker-Glenn, Charles A. G.; Kempson, James; Walker, Gary M.; Yee, James G. K. [Organic and Biomolecular Chemistry, 2008, vol. 6, # 8, p. 1478 - 1497]
[2]Kozikowski, Alan P.; Stein, Philip D. [Journal of Organic Chemistry, 1984, vol. 49, # 13, p. 2301 - 2309]
[3]Yadav, J. S.; Praveen Kumar, T. K.; Maniyan, P. P. [Tetrahedron Letters, 1993, vol. 34, # 18, p. 2969 - 2972]
[4]Schomaker, Jennifer M.; Pulgam, Veera Reddy; Borhan, Babak [Journal of the American Chemical Society, 2004, vol. 126, # 42, p. 13600 - 13601]
[5]Chattopadhyay, Shital K.; Pattenden, Gerald [Journal of the Chemical Society. Perkin Transactions 1 (2001), 2000, # 15, p. 2429 - 2454]
[6]Nagaiah, Burea; Narsaiah, Akkirala Venkat [Helvetica Chimica Acta, 2013, vol. 96, # 10, p. 1948 - 1954]
[7]Baranov, Mikhail S.; Kaskova, Zinaida M.; Gritсenko, Roman; Postikova, Svetlana G.; Ivashkin, Pavel E.; Kislukhin, Alexander A.; Moskvin, Dmitrii I.; Mineev, Konstantin S.; Arseniev, Alexander S.; Labas, Yulii A.; Yampolsky, Ilia V. [Synlett, 2017, vol. 28, # 5, p. 583 - 588]

9
[ 19790-60-4 ]
[ 1066-54-2 ]
[ 700380-30-9 ]

Yield	Reaction Conditions	Operation in experiment
93%	Stage #1: trimethylsilylacetylene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Stage #2: 3-Benzyloxypropanal In tetrahydrofuran; hexane at -78 - 0℃; for 3h;
93%	Stage #1: trimethylsilylacetylene With n-butyllithium In tetrahydrofuran; hexane at -20 - 20℃; for 0.166667h; Inert atmosphere; Stage #2: 3-Benzyloxypropanal In tetrahydrofuran; hexane at -20 - 20℃; for 3h; Inert atmosphere;
	With ethylmagnesium bromide Multistep reaction;

Stage #1: trimethylsilylacetylene With n-butyllithium In tetrahydrofuran; hexane at -78 - -20℃; Stage #2: 3-Benzyloxypropanal In tetrahydrofuran; hexane at -78℃; for 1h; Further stages.;

Reference： [1]Takimoto, Masanori; Kawamura, Mitsunobu; Mori, Miwako [Synthesis, 2004, # 5, p. 791 - 795]
[2]Fukumoto, Yoshiya; Okazaki, Natsuki; Chatani, Naoto [Organic Letters, 2019, vol. 21, # 6, p. 1760 - 1765]
[3]Mandai, Tadakatsu; Tsuji, Jiro; Tsujiguchi, Yoshikazu; Saito, Sciki [Journal of the American Chemical Society, 1993, vol. 115, # 13, p. 5865 - 5866]
[4]Diaz, David D.; Ramirez, Miguel A.; Martin, Victor S. [Chemistry - A European Journal, 2006, vol. 12, # 9, p. 2593 - 2606]

10
[ 19790-60-4 ]
[ 149-73-5 ]
[ 34591-97-4 ]

Yield	Reaction Conditions	Operation in experiment
	With magnesium sulfate; toluene-4-sulfonic acid; In methanol; dichloromethane; at -78 - 20℃;	General procedure: A solution of 4 (1.00 mmol) in dichloromethane (5 mL) and MeOH (5 mL) was cooled to -78 C using a dry ice/acetone bath. Then, ozone was bubbled through the reaction mixture for 10 min. After the ozonolysis was completed, the reaction mixture was quenched with dimethyl sulfide (0.5 mL, 6.5 mmol) at -78 C, and p-toluenesulfonic acid monohydrate (19 mg, 0.10 mmol), MgSO4 (1.0 g), and trimethyl orthoformate (3.0 mL) were added to the reaction mixture. The reaction mixture was allowed to warm up to room temperature, and stirred for overnight. Then, the reaction mixture was filtered and concentrated on a rotary evaporator under reduced pressure. The resulting crude oil was purified by silica gel column chromatography to afford 9 in 48-79% yields.

Reference： [1]Synthesis,2011,p. 3965 - 3974
[2]Journal of Organic Chemistry,1991,vol. 56,p. 5755 - 5758
[3]Tetrahedron,2020,vol. 76

11
[ 867-13-0 ]
[ 19790-60-4 ]
[ 70542-83-5 ]

Yield	Reaction Conditions	Operation in experiment
90.3%	With potassium carbonate In di-isopropyl ether; water at 0 - 20℃; for 66h;	23.2 (Step 2) ethyl (E)-5-benzyloxypent-2-enonate An aqueous solution 95mL of potassium carbonate 86.9g (629mmol) was cooled to 0 ° C, the mixture was stirred for 2 diethoxyphosphoryl ethyl acetate 63.0mL (71.2g, 318mmol) were added for 15 minutes at 0 ° C. Then, after stirring diisopropyl ether 110mL solution was synthesized in Step 1 3-benzyloxy propanal 39.3 g (239 mmol) was added over 6 min 5 min and stirred for 66 hours then warmed to room temperature. And the 200mL of water was added to the reaction mixture was extracted twice with diethyl ether, and dried over anhydrous sodium sulfate and the combined organic layer. The residue and the solvent was evaporated silica gel column chromatography (Biotage, elution solvent; hexane / ethyl acetate = 99 / 1-75 / 25) to obtain the title compound 50.7g (the 90.3% yield) as an oily substance.
87%	With potassium carbonate In diethyl ether; water at 0 - 20℃; Inert atmosphere;
86%	With potassium carbonate In diethyl ether; water at 0 - 20℃;

81%	With sodium hydride In benzene at 0℃; for 1h;
72%	With 1,8-diazabicyclo[5.4.0]undec-7-ene; lithium chloride In acetonitrile
6.80 g	With sodium hydride In tetrahydrofuran at 0℃; for 0.5h;

Reference： [1]Current Patent Assignee: DAIICHI SANKYO COMPANY, LIMITED - JP2016/56134, 2016, A Location in patent: Paragraph 0227; 0228; 0229; 0231
[2]Location in patent: scheme or table Heapy, Amanda M.; Brimble, Margaret A. [Tetrahedron, 2010, vol. 66, # 29, p. 5424 - 5431]
[3]Heapy, Amanda M.; Wagner, Thomas W.; Brimble, Margaret M. [Synlett, 2007, # 15, p. 2359 - 2362]
[4]Davis, Franklin A.; Qi, Hongyan; Sundarababu, Gajendran [Tetrahedron, 2000, vol. 56, # 30, p. 5303 - 5310]
[5]Weltering, Thomas J.; Weitz-Schmidt, Gabriele; Wong, Chi-Huey [Tetrahedron Letters, 1996, vol. 37, # 50, p. 9033 - 9036]
[6]Azzena, Francesca; Calvani, Federico; Crotti, Paolo; Gardelli, Cristina; Macchia, Franco; Pineschi, Mauro [Tetrahedron, 1995, vol. 51, # 38, p. 10601 - 10626]

12
[ 19790-60-4 ]
[ 281190-96-3 ]
[ 281190-97-4 ]

Yield	Reaction Conditions	Operation in experiment
98%	Stage #1: (3E,1'R,2'S)-1'-[(p-tolylsulfonyl)amino]indan-2-yl 4-phenylbut-3-enoate With titanium tetrachloride; N-isopropylethylamine In dichloromethane at 20℃; for 1h; Stage #2: 3-Benzyloxypropanal With titanium tetrachloride In dichloromethane at -78℃; for 0.333333h;
98%	Stage #1: (3E,1'R,2'S)-1'-[(p-tolylsulfonyl)amino]indan-2-yl 4-phenylbut-3-enoate With titanium tetrachloride; N-ethyl-N,N-diisopropylamine In dichloromethane at 0 - 23℃; for 1h; Stage #2: 3-Benzyloxypropanal at -78℃; for 0.333333h; Further stages.;
98%	With titanium tetrachloride; N-ethyl-N,N-diisopropylamine

Reference： [1]Ghosh, Arun K.; Bischoff [European Journal of Organic Chemistry, 2004, # 10, p. 2131 - 2141]
[2]Ghosh; Bischoff [Organic letters, 2000, vol. 2, # 11, p. 1573 - 1575]
[3]Location in patent: scheme or table Ghosh, Arun K.; Dawson, Zachary L. [Synthesis, 2009, # 17, p. 2992 - 3002]

13
[ 70388-33-9 ]
[ 19790-60-4 ]

Yield	Reaction Conditions	Operation in experiment
86%	Stage #1: 4-benzyloxybut-1-ene With ozone In dichloromethane at -78℃; Stage #2: With triphenylphosphine
76%	Stage #1: 4-benzyloxybut-1-ene With ozone In dichloromethane at -78℃; for 2h; Stage #2: With triphenylphosphine In dichloromethane at 20℃; for 16h;
76%	Stage #1: 4-benzyloxybut-1-ene With ozone In dichloromethane at -78℃; for 2h; Stage #2: With triphenylphosphine In dichloromethane at 20℃; for 16h;	3-(benzyioxy)propanai (38): Compound 38 was synthesized following a reported protocol. (Flowers, C. L.; Vogel, P. Chem. - A Eur. 1 2010, 16(47), 14074-14082)

65%	Stage #1: 4-benzyloxybut-1-ene With ozone In methanol; dichloromethane at -78℃; Stage #2: With dimethylsulfide In methanol; dichloromethane at -78 - 20℃;	3-Benzyloxy-propionaldehyde [6g] A solution of the benzyl ether derivative described above (9.24mmol, 1eq) in CH2Cl2/MeOH (135/15 mL) was poured in a long neck flask, and cooled to -78°C under argon. The mixture was saturated with O3 until the solution became blue. Excess ozone was flushed with argon until colour disappeared. Me2S (10 eq) was then added, and the mixture was allowed to reach slowly room temperature and stirred overnight. It was washed with brine, dried over anhydrous MgSO4, filtered and concentrated in vacuo. After purification by column chromatography on silica gel (EP/ CH2Cl2; 50:50 to CH2Cl2) aldehyde 6i (0.99 g, 65%) was obtained as a colourless oil.
61%	With sodium periodate; osmium(VIII) oxide In tetrahydrofuran; <i>tert</i>-butyl alcohol
	Stage #1: 4-benzyloxybut-1-ene With ozone Stage #2: With triethylamine Further stages.;
	Multi-step reaction with 2 steps 1: 74 percent / aq. KMnO₄ / acetone / 0 °C 2: 95 percent / aq. NaIO₄ / tetrahydrofuran / Ambient temperature
	Stage #1: 4-benzyloxybut-1-ene With ozone In dichloromethane at -78℃; for 0.166667h; Stage #2: With oxygen In dichloromethane at -78℃; for 0.166667h; Stage #3: With triphenylphosphine In dichloromethane at -78 - 25℃; Inert atmosphere;
	Multi-step reaction with 2 steps 1: osmium(VIII) oxide; water; 4-methylmorpholine N-oxide / tetrahydrofuran; acetonitrile / 20 °C 2: periodic acid / tetrahydrofuran / 2 h / 20 °C / Inert atmosphere

Reference： [1]Hon, Yung-Son; Lu, Ling; Chang, Rong-Chi; Lin, Sheng-Wun; Sun, Pei-Pei; Lee, Chia-Fu [Tetrahedron, 2000, vol. 56, # 47, p. 9269 - 9279]
[2]Koyanagi, Takaoki; Leriche, Geoffray; Onofrei, David; Holland, Gregory P.; Mayer, Michael; Yang, Jerry [Angewandte Chemie - International Edition, 2016, vol. 55, # 5, p. 1890 - 1893][Angew. Chem., 2015, p. 1922 - 1925,4]
[3]Current Patent Assignee: UNIVERSITY OF CALIFORNIA - WO2017/40702, 2017, A1 Location in patent: Paragraph 0450; 0463; 0464
[4]Chalopin, Thibaut; Jebali, Khaoula; Gaulon-Nourry, Catherine; Dénès, Fabrice; Lebreton, Jacques; Mathé-Allainmat, Monique [Tetrahedron, 2016, vol. 72, # 2, p. 318 - 327]
[5]Pedersen, Christian Marcus; Marinescu, Lavinia Georgeta; Bols, Mikael [Organic and Biomolecular Chemistry, 2005, vol. 3, # 5, p. 816 - 822]
[6]Hon, Yung-Son; Wong, Ying-Chieh; Chang, Chun-Ping; Hsieh, Cheng-Han [Tetrahedron, 2007, vol. 63, # 46, p. 11325 - 11340]
[7]Matsumoto, Kazutsugu; Fuwa, Seiji; Shimojo, Megumi; Kitajima, Hidehiko [Bulletin of the Chemical Society of Japan, 1996, vol. 69, # 10, p. 2977 - 2987]
[8]Flowers, Christopher L.; Vogel, Pierre [Chemistry - A European Journal, 2010, vol. 16, # 47, p. 14074 - 14082]
[9]Borg, Tessie; Tuzina, Pavel; Somfai, Peter [Journal of Organic Chemistry, 2011, vol. 76, # 19, p. 8070 - 8075]

14
[ 19790-60-4 ]
[ 175441-30-2 ]
[ 503620-03-9 ]

Yield	Reaction Conditions	Operation in experiment
90%	Stage #1: 3-Benzyloxypropanal; (1R,2S)-1-(N-tosylamino)-2-indanyl propionate With titanium tetrachloride; N-ethyl-N,N-diisopropylamine In dichloromethane at 0 - 23℃; Stage #2: 3-Benzyloxypropanal With titanium tetrachloride In dichloromethane at -78℃; for 2h; Further stages.;
90%	With titanium tetrachloride; N-ethyl-N,N-diisopropylamine

Reference： [1]Ghosh, Arun K.; Liu, Chunfeng [Journal of the American Chemical Society, 2003, vol. 125, # 9, p. 2374 - 2375]
[2]Location in patent: scheme or table Ghosh, Arun K.; Dawson, Zachary L. [Synthesis, 2009, # 17, p. 2992 - 3002]

15
[ 19790-60-4 ]
[ 586-96-9 ]
[ 771476-38-1 ]

Yield	Reaction Conditions	Operation in experiment
76%	With <i>L</i>-proline In dimethyl sulfoxide at 20℃;
	With rac-Pro-OH In dimethyl sulfoxide at 20℃;
	With <i>L</i>-proline In dimethyl sulfoxide at 20℃; for 0.166667h;

With <i>L</i>-proline In chloroform at 0℃; for 0.666667h; enantioselective reaction;

Reference： [1]Cordova, Armando; Sunden, Henrik; Bogevig, Anders; Johansson, Mikael; Himo, Fahmi [Chemistry - A European Journal, 2004, vol. 10, # 15, p. 3673 - 3684]
[2]Zhong, Guofu [Angewandte Chemie - International Edition, 2003, vol. 42, # 35, p. 4247 - 4250]
[3]Zhong, Guofu; Yu, Yongping [Organic Letters, 2004, vol. 6, # 10, p. 1637 - 1639]
[4]Lin, Hua; Sun, Xing-Wen; Lin, Guo-Qiang [Organic Letters, 2014, vol. 16, # 3, p. 752 - 755]

16
[ 19790-60-4 ]
[ 694527-37-2 ]
(2S,3R,5S)-2,5-Bis-(2-benzyloxy-ethyl)-3-vinyl-tetrahydro-furan [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
52%	With boron trifluoride diethyl etherate In dichloromethane at -78 - 20℃; for 9h;

Reference： [1]Sarkar, Tarun K.; Haque, Sk. Anwarul; Basak, Arindrajit [Angewandte Chemie - International Edition, 2004, vol. 43, # 11, p. 1417 - 1419]

17
[ 865-50-9 ]
[ 19790-60-4 ]
[ 858970-90-8 ]

Yield	Reaction Conditions	Operation in experiment
90%	Stage #1: iodomethane-d3 With magnesium In diethyl ether Stage #2: 3-Benzyloxypropanal In diethyl ether at 20℃;
70%	Stage #1: iodomethane-d3 With magnesium In diethyl ether Stage #2: 3-Benzyloxypropanal In diethyl ether at 0 - 20℃;

Reference： [1]Dickschat, Jeroen S.; Bode, Helge B.; Mahmud, Taifo; Mueller, Rolf; Schulz, Stefan [Journal of Organic Chemistry, 2005, vol. 70, # 13, p. 5174 - 5182]
[2]Location in patent: experimental part Dickschat, Jeroen S.; Citron, Christian A.; Brock, Nelson L.; Riclea, Ramona; Kuhz, Henning [European Journal of Organic Chemistry, 2011, # 18, p. 3339 - 3346]

18
[ 945736-77-6 ]
[ 19790-60-4 ]
[ 853193-61-0 ]

Yield	Reaction Conditions	Operation in experiment
73%	With toluene-4-sulfonic acid In dichloromethane at 20℃; for 48h;

Reference： [1]Sammakia, Tarek; Johns, Deidre M.; Kim, Ganghyeok; Berliner, Martin A. [Journal of the American Chemical Society, 2005, vol. 127, # 18, p. 6504 - 6505]

19
[ 19790-60-4 ]
(3R)-3-propionyl-4-benzyloxazolidin-2-one [ No CAS ]
[ 870091-89-7 ]

Yield	Reaction Conditions	Operation in experiment
97%	With 1-methyl-pyrrolidin-2-one; titanium tetrachloride; N-ethyl-N,N-diisopropylamine In dichloromethane at -5 - 20℃; for 3.5h;
97%	Stage #1: (3R)-3-propionyl-4-benzyloxazolidin-2-one With di-n-butylboryl trifluoromethanesulfonate; triethylamine In dichloromethane at -78℃; Inert atmosphere; Stage #2: 3-Benzyloxypropanal In dichloromethane at -78 - 0℃; Inert atmosphere; stereoselective reaction;
92%	With di-n-butylboryl trifluoromethanesulfonate; N-ethyl-N,N-diisopropylamine

92%	Stage #1: (3R)-3-propionyl-4-benzyloxazolidin-2-one With di-n-butylboryl trifluoromethanesulfonate; triethylamine In dichloromethane at 0℃; Stage #2: 3-Benzyloxypropanal In dichloromethane at -78 - 0℃; Stage #3: With methanol; dihydrogen peroxide at 20℃; for 1h; aq. phosphate buffer;
90%	Stage #1: (3R)-3-propionyl-4-benzyloxazolidin-2-one With di-n-butylboryl trifluoromethanesulfonate; N-ethyl-N,N-diisopropylamine In dichloromethane at 0℃; for 0.833333h; Stage #2: 3-Benzyloxypropanal In dichloromethane at -78 - 20℃; for 3.66667h; Stage #3: With dihydrogen peroxide In methanol at 20℃; for 0.5h; stereospecific reaction;	Evans Aldol Product 17 A solution of oxazolidinone 16 (40.8 g, 175 mmol, 1.00 equiv) in CH2Cl2 (700 mL) was cooled to 0 °C and Bu2BOTf (210 mL, 1.0 M in CH2Cl2, 210 mmol, 1.20 equiv) was added over the course of 30 min. Subsequently, iPr2NEt (41.6 mL, 31.6 g, 245 mmol, 1.40 equiv) was added over the course of 10 min. The solution was stirred a further 10 min and then cooled to -78 °C. A solution of 3-(benzyloxy)propanal(33.6 g, 205 mmol, 1.17 equiv) in CH2Cl2 (70 mL) was added over the course of 10 min and the reaction was stirred for 2 h at -78 °C and 1.5 h at 0 °C. Subsequently, the reaction was quenched by addition of aq pH 7 buffer (225 mL) and MeOH (325 mL). After stirring for 30 min, MeOH (450 mL) and H2O2 (30%, 225 mL) were added and stirring was continued for 30 min at r.t. The layers were separated and the aqueouslayer was extracted with CH2Cl2 (3 × 250 mL). The organic layers were combined, washed with sat. aq NaHCO3 solution (280 mL) andsat. aq NaCl solution (390 mL), and dried (Na2SO4). The solvent was removed under reduced pressure and the residue was purified with flash column chromatography (silica, pentane/Et2O 1:1 → 0:1), to afford alcohol 17 as a colorless oil (67.2 g, 97%). Rf = 0.10 (pentane/Et2O, 1:1) [UV, KMnO4]. 1H NMR (500 MHz, CDCl3): = 1.29 (d, 3J = 7.0 Hz, 3 H, CH3-44), 1.75(dddd, 2J = 14.3 Hz, 3J = 6.6, 4.7, 3.0 Hz, 1 H, CHH-20), 1.88 (dddd, 2J =14.3 Hz, 3J = 9.4, 7.3, 4.8 Hz, 1 H, CHH-20), 2.78 (dd, 2J = 13.4 Hz, 3J =9.5 Hz, 1 H, CHCHHAr), 3.26 (dd, 2J = 13.4 Hz, 3J = 3.4 Hz, 1 H, CHCHHAr),3.31 (d, 3J = 2.4 Hz, 1 H, OH), 3.59-3.73 (m, 2 H, CH2OCO), 3.80-3.87 (m, 1 H, CH-22), 4.16-4.21 (m, 3 H, CH2-19, CH-21), 4.52 (s, 2 H,OCH2Ar), 4.68 (ddt, 3J = 9.5, 6.8, 3.4 Hz, 1 H, CHN), 7.19-7.21 (m, 2 H,CHAr), 7.26-7.36 (m, 8 H, CHAr). 13C NMR (101 MHz, CDCl3): = 11.3 (q, CH3-44), 33.9 (t, CH2-20), 38.0(t, CHCH2Ar), 42.7 (d, CH-22), 55.4 (d, CHN), 66.3 (t, CH2-19), 68.5 (t,CH2OCO), 70.6 (d, CH-21), 73.4 (t, OCH2Ar), 127.5 (d, CHAr), 127.8 (d,CHAr), 127.8 (d, CHAr), 128.6 (d, CHAr), 129.1 (d, CHAr), 129.6 (d, CHAr),135.3 (s, CAr), 138.2 (s, CAr), 153.2 (s, OCO), 176.8 (s, C-23).The analytical data matched those reported in the literature.[66]
86%	With titanium tetrachloride; (-)-sparteine In dichloromethane at 0℃; for 2h; stereoselective reaction;
82%	With di-n-butylboryl trifluoromethanesulfonate; triethylamine In dichloromethane at -78℃; for 0.5h;
80%	Stage #1: (3R)-3-propionyl-4-benzyloxazolidin-2-one With di-n-butylboryl trifluoromethanesulfonate; triethylamine In dichloromethane for 0.666667h; Cooling; Stage #2: 3-Benzyloxypropanal In dichloromethane at -77 - 0℃; for 3.5h; Stage #3: With phosphate buffer; dihydrogen peroxide In dichloromethane at 0℃; for 0.5h;
79%	Stage #1: (3R)-3-propionyl-4-benzyloxazolidin-2-one With di-n-butylboryl trifluoromethanesulfonate; triethylamine In dichloromethane at -50 - 0℃; for 0.333333h; Inert atmosphere; Stage #2: 3-Benzyloxypropanal In dichloromethane at -75 - 0℃; for 3h; Inert atmosphere;
72%	Stage #1: (3R)-3-propionyl-4-benzyloxazolidin-2-one With di-n-butylboryl trifluoromethanesulfonate; triethylamine In dichloromethane at -78 - 0℃; for 1.5h; Stage #2: 3-Benzyloxypropanal In dichloromethane at -78 - 20℃; for 4h; Further stages.;
72%	Stage #1: (3R)-3-propionyl-4-benzyloxazolidin-2-one With di-n-butylboryl trifluoromethanesulfonate; triethylamine In dichloromethane at -78 - 0℃; Inert atmosphere; Stage #2: 3-Benzyloxypropanal In dichloromethane at -78 - 20℃; for 4h;

Reference： [1]Tian, Hua; Jiao, Xiaozhen; Xie, Ping; Liang, Xiaotian [Tetrahedron Letters, 2005, vol. 46, # 49, p. 8579 - 8581]
[2]Kishi, Takayuki; Fujisawa, Yuka; Takamura, Hiroyoshi; Kadota, Isao [Heterocycles, 2014, vol. 89, # 2, p. 515 - 522]
[3]Nyavanandi, Vijay Kumar; Nanduri, Srinivas; Dev, R. Vasu; Naidu, Andra; Iqbal, Javed [Tetrahedron Letters, 2006, vol. 47, # 37, p. 6667 - 6672]
[4]Location in patent: experimental part Tsutsumi, Ryosuke; Kuranaga, Takefumi; Wright, Jeffrey L.C.; Baden, Daniel G.; Ito, Emiko; Satake, Masayuki; Tachibana, Kazuo [Tetrahedron, 2010, vol. 66, # 34, p. 6775 - 6782]
[5]Wienhold, Sebastian; Fritz, Lukas; Judt, Tatjana; Hackl, Sabrina; Neubauer, Thomas; Sauerer, Bastian; Bach, Thorsten [Synthesis, 2021, vol. 53, # 22, p. 4246 - 4262]
[6]Jithender Reddy, V.; Pradhan, Tapan Kumar; Ghosh, Subhash [Tetrahedron Letters, 2012, vol. 53, # 45, p. 6148 - 6150,3]
[7]Sabitha, Gowravaram; Padmaja; Reddy, K. Bhaskar; Yadav [Tetrahedron Letters, 2008, vol. 49, # 5, p. 919 - 922]
[8]Rauhala, Vesa; Naettinen, Kalle; Rissanen, Kari; Koskinen, Ari M. P. [European Journal of Organic Chemistry, 2005, # 19, p. 4119 - 4126]
[9]Location in patent: experimental part Bauder, Claude [European Journal of Organic Chemistry, 2010, # 32, p. 6207 - 6216]
[10]Pattenden, Gerald; Ashweek, Neil J.; Baker-Glenn, Charles A. G.; Walker, Gary M.; Yee, James G. K. [Angewandte Chemie - International Edition, 2007, vol. 46, # 23, p. 4359 - 4363]
[11]Pattenden, Gerald; Ashweek, Neil J.; Baker-Glenn, Charles A. G.; Kempson, James; Walker, Gary M.; Yee, James G. K. [Organic and Biomolecular Chemistry, 2008, vol. 6, # 8, p. 1478 - 1497]

20
[ 70388-33-9 ]
[ 19790-60-4 ]
[ 6278-91-7 ]

Yield	Reaction Conditions	Operation in experiment
80%	With oxygen; 1-butyl-3-methylimidazolium Tetrafluoroborate In water at 60℃; for 25h;

Reference： [1]Ansari; Joyasawal, Sipak; Gupta, Manoj K.; Yadav; Gree [Tetrahedron Letters, 2005, vol. 46, # 44, p. 7507 - 7510]

21
[ 19790-60-4 ]
[ 125664-95-1 ]
[ 899798-72-2 ]

Reference： [1]Organic Letters,2006,vol. 8,p. 2695 - 2698

22
hepta-5,6-dienoic acid benzyl ester [ No CAS ]
[ 19790-60-4 ]
(R)-2-((R)-3-Benzyloxy-1-hydroxy-propyl)-hepta-5,6-dienoic acid benzyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
69%	Stage #1: hepta-5,6-dienoic acid benzyl ester With triethylamine; dicyclohexyl(((trifluoromethyl)sulfonyl)oxy)borane In dichloromethane at -78℃; Stage #2: 3-Benzyloxypropanal at -78 - 0℃; Further stages.;

Reference： [1]Amarasinghe, Kande K. D.; Montgomery, John [Journal of the American Chemical Society, 2002, vol. 124, # 32, p. 9366 - 9367]

23
[ 457060-28-5 ]
[ 19790-60-4 ]
2-(3-benzyloxy-1-hydroxy-propyl)-hepta-5,6-dienoic acid-2-[benzyl-(2,4,6-trimethyl-benzenesulfonyl)-amino]-1-phenyl-propyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
72%	Stage #1: hepta-5,6-dienoic acid 2-[benzyl-(2,4,6-trimethyl-benzenesulfonyl)-amino]-1-phenyl-propyl ester With triethylamine; dicyclohexyl(((trifluoromethyl)sulfonyl)oxy)borane In hexane; dichloromethane at -78℃; for 2h; Stage #2: 3-Benzyloxypropanal In hexane; dichloromethane at -78 - 0℃; Further stages.;

Reference： [1]Amarasinghe, Kande K. D.; Montgomery, John [Journal of the American Chemical Society, 2002, vol. 124, # 32, p. 9366 - 9367]

24
[ 910545-65-2 ]
[ 19790-60-4 ]
(S)-1-(benzyloxy)hex-5-en-3-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87%	With camphor-10-sulfonic acid In 1,2-dichloro-ethane at 0℃; for 24h;

Reference： [1]Sugiura, Masaharu; Mori, Chieko; Kobayashi, Shu [Journal of the American Chemical Society, 2006, vol. 128, # 34, p. 11038 - 11039]

25
[ 13865-20-8 ]
[ 19790-60-4 ]
[ 1730-25-2 ]
[ 933039-90-8 ]
C₁₉H₂₇O₄Br [ No CAS ]

Reference： [1]Chemical Communications,2007,p. 939 - 941

26
[ 31469-16-6 ]
[ 19790-60-4 ]
[ 944393-40-2 ]

Reference： [1]Organic Letters,2007,vol. 9,p. 2597 - 2600
[2]Synthesis,2009,p. 2855 - 2872

27
[ 31469-16-6 ]
[ 19790-60-4 ]
[ 944393-40-2 ]
C₁₉H₃₂O₄Si [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		To a solution of ligand 13 (2.12 g, 5.4 mmol) in propylnitrile (40 ml) was added BH3THF complex (5.4 ml, 5.4 mmol) at rt and the mixture was stirred at 45 0C for 1 h before cooled to -78 0C. Ketene acetal 10 (7.71 g, 41 mmol) was then added at -78 0C, followed by the addition of aldehyde 9 (4.43 g, 27 mmol) as a solution in propylnitrile (10 ml) over 4 h via syringe pump. The reaction was stirred for another 2 h before quenched with pH 7 buffer (50 ml). The reaction mixture was warmed to room temperature and diluted with EtOAc, the organic solution was washed with NaHCO3, dried over Na2SO4 and concentrated. The residue was purified by FC to give a mixture of TMS protected hydroxyl ester and free hydroxyl ester. The TMS protected product was treated with 2.0 M HCI/Et2O (2.0 eq.) at 0 0C for 1 h at room temperature. The reaction was directly concentrated and purified by FC to give 10a (combined 7.16 g, 95%): [α]20D + 15.95 (c = 0.5, DCM).1HNMR (CDCI3) δ 7.34-7.26 (m, 5H), 4.53 (d, J = 12.0 Hz, 1 H), 4.14 (q, J = 7.0 Hz, 2H), 3.91 -3.89 (m, 1 H), 3.75-3.65 (m, 2H), 3.16 (br, 1 H), 1.75-1.65 (m, 2H), 1.26 (t, J = 7.0 Hz, 3H), 1.19 (s, 3H), 1.17 (s, 3H); 13C NMR (CDCI3) δ 177.5, 138.2, 128.6, 128.4, 128.0, 127.8, 77.7, 75.5, 73.5, 69.4, 60.7, 47.0, 31.7, 21.8, 20.6, 18.1 , 14.3.

Reference： [1]Organic Letters,2007,vol. 9,p. 2597 - 2600
[2]Patent: WO2009/158381,2009,A1 .Location in patent: Page/Page column 123

28
[ 19790-60-4 ]
[ 513-31-5 ]
C₁₃H₁₇BrO₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With tin; hydrogen bromide In diethyl ether; water at 20℃; for 4h;
74%	With tin; hydrogen bromide In diethyl ether at 20℃;

Reference： [1]Li, Linjie; Sun, Xianwei; He, Yanyang; Gao, Lu; Song, Zhenlei [Chemical Communications, 2015, vol. 51, # 80, p. 14925 - 14928]
[2]Fang, Yewen; Li, Chaozhong [Journal of the American Chemical Society, 2007, vol. 129, # 26, p. 8092 - 8093]

29
[ 19790-60-4 ]
[ 5044-52-0 ]
[ 586-96-9 ]
(6S)-6-(benzyloxymethyl)-2-phenyl-3,6-dihydro-2H-1,2-oxazine [ No CAS ]

Reference： [1]Organic and Biomolecular Chemistry,2007,vol. 5,p. 2678 - 2689

30
[ 19790-60-4 ]
[ 111466-55-8 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: CH₂Cl₂ / 36 h / 20 °C 2: 92 percent / diisobutylaluminum hydride / tetrahydrofuran; toluene / 3 h / -20 °C 3: diethyl (-)-tartrate; Ti(O-iPr)4; tBuOOH / molecular sieves 4A / CH₂Cl₂; toluene / 13 h / -23 - -12 °C
	Multi-step reaction with 3 steps 1.1: 28 g / CH₂Cl₂ / 20 °C 2.1: 84 percent / DIBAL-H / tetrahydrofuran; hexane / 2 h / 0 °C 3.1: (+)-diethyl tartrate; 4-Angstroem molecular sieves / Ti(OiPr)4 / CH₂Cl₂ / 0.5 h / -20 °C 3.2: 76 percent / t-BuOOH / CH₂Cl₂; 2,2,4-trimethyl-pentane / 20 h / -20 - -18 °C
	Multi-step reaction with 3 steps 1: benzene 2: DIBAL-H / CH₂Cl₂ / -10 °C 3: (+)-DET, titanium tetraisopropoxide (TIP), tertiary butylhydroperoxide (TBHP), molecular sieves / CH₂Cl₂ / -25 °C

	Multi-step reaction with 3 steps 2: 90 percent / DIBAL-H / citric acid / diethyl ether; hexane / -78 - 0 °C / -78 deg C to room temp. 3: Ti(O-i-Pr)4, (-)-diisopropyl tartrate, t-BuOOH / CH₂Cl₂ / 1.) -23 deg C, 5 min, 2.) -20 deg C, 20 h
	Multi-step reaction with 3 steps 1: benzene / 3 h / 20 °C / Inert atmosphere 2: diisobutylaluminium hydride / dichloromethane / Inert atmosphere 3: diethyl (2R,3R)-tartrate; titanium(IV) isopropylate; tert.-butylhydroperoxide / dichloromethane / -20 °C / Molecular sieve; Inert atmosphere
	Multi-step reaction with 3 steps 1: lithium hydroxide / tetrahydrofuran / Reflux 2: diisobutylaluminium hydride / tetrahydrofuran / -40 °C 3: tert.-butylhydroperoxide; titanium(IV) isopropylate; diethyl (2R,3R)-tartrate / dichloromethane / -20 °C

Reference： [1]Schomaker, Jennifer M.; Pulgam, Veera Reddy; Borhan, Babak [Journal of the American Chemical Society, 2004, vol. 126, # 42, p. 13600 - 13601]
[2]Chattopadhyay, Shital K.; Pattenden, Gerald [Journal of the Chemical Society. Perkin Transactions 1 (2001), 2000, # 15, p. 2429 - 2454]
[3]Yadav, J. S.; Praveen Kumar, T. K.; Maniyan, P. P. [Tetrahedron Letters, 1993, vol. 34, # 18, p. 2969 - 2972]
[4]Kozikowski, Alan P.; Stein, Philip D. [Journal of Organic Chemistry, 1984, vol. 49, # 13, p. 2301 - 2309]
[5]Nagaiah, Burea; Narsaiah, Akkirala Venkat [Helvetica Chimica Acta, 2013, vol. 96, # 10, p. 1948 - 1954]
[6]De Angelis, Martina; Primitivo, Ludovica; Lizzio, Federica; Agostinelli, Sonia; Sappino, Carla; Ben Romdan, Ilaria; Bonanni, Luciano; D'Annibale, Andrea; Antonioletti, Roberto; Ricelli, Alessandra; Righi, Giuliana [Carbohydrate Research, 2022, vol. 511]

31
[ 19790-60-4 ]
[ 89956-14-9 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: CH₂Cl₂ / 36 h / 20 °C 2: 92 percent / diisobutylaluminum hydride / tetrahydrofuran; toluene / 3 h / -20 °C 3: diethyl (-)-tartrate; Ti(O-iPr)4; tBuOOH / molecular sieves 4A / CH₂Cl₂; toluene / 13 h / -23 - -12 °C
	Multi-step reaction with 3 steps 1.1: 28 g / CH₂Cl₂ / 20 °C 2.1: 84 percent / DIBAL-H / tetrahydrofuran; hexane / 2 h / 0 °C 3.1: Ti(O-i-Pr)4; (-)-diethyl tartrate; 4 Angstroem molecular sieves / CH₂Cl₂ / 0.5 h / -20 °C 3.2: 61 percent / t-BuOOH / CH₂Cl₂; 2,2,4-trimethyl-pentane / -20 °C
	Multi-step reaction with 3 steps 1: 81 percent / CH₂Cl₂ / 5 h / Ambient temperature 2: 86 percent / Dibal-H / toluene / 4 h / -78 °C 3: 80 percent / D-(-)diethyltartrate, Ti(OiPr)4, t-BuOOH / CH₂Cl₂ / 12 h / -25 °C

Multi-step reaction with 3 steps 2: 90 percent / DIBAL-H / citric acid / diethyl ether; hexane / -78 - 0 °C / -78 deg C to room temp. 3: 81 percent / Ti(O-i-Pr)4, (-)-diisopropyl tartrate, t-BuOOH / CH₂Cl₂ / 1.) -23 deg C, 5 min, 2.) -20 deg C, 20 h

Reference： [1]Schomaker, Jennifer M.; Pulgam, Veera Reddy; Borhan, Babak [Journal of the American Chemical Society, 2004, vol. 126, # 42, p. 13600 - 13601]
[2]Chattopadhyay, Shital K.; Pattenden, Gerald [Journal of the Chemical Society. Perkin Transactions 1 (2001), 2000, # 15, p. 2429 - 2454]
[3]Diez-Martin, David; Kotecha, Nikesh R.; Ley, Steven V.; Mantegani, Sergio; Menendez, J. Carlos; Organ, Helen M.; White, Andrew D.; Banks, Bernard J. [Tetrahedron, 1992, vol. 48, # 37, p. 7899 - 7938]
[4]Kozikowski, Alan P.; Stein, Philip D. [Journal of Organic Chemistry, 1984, vol. 49, # 13, p. 2301 - 2309]

32
[ 19790-60-4 ]
[ 27912-85-2 ]

Reference： [1]Chemistry Letters,1986,p. 1385 - 1388
[2]ChemPlusChem,2016,vol. 81,p. 1160 - 1165

33
[ 19790-60-4 ]
[ 352-13-6 ]
[ 213201-61-7 ]

Yield	Reaction Conditions	Operation in experiment
44%	In tetrahydrofuran at 0 - 20℃; for 1h;	3.B Example 3; Preparation of 1-(Aryl)-Propane-1,3-Diol from Propane-1,3-Diol via Grignard Addition [0295] Step A: (J. Org. Chem. 53:911 (1988)) [0296] To a solution of oxalyl chloride (5.7 mL, 97 mmol) in dichloromethane (200 mL) at -78° C. was added dimethyl sulfoxide (9.2 mL, 130 mmol). The reaction mixture was stirred at -78° C. for 20 min before addition of 3-(benzyloxy)propan-1-ol (11 g, 65 mmol) in dichloromethane (25 mL). After an hour at -78° C., reaction was quenched with triethylamine (19 mL, 260 mmol) and warmed to room temperature. Work-up and column chromatography by elution with dichloromethane resulted in 8 g (75%) of 3-(benzyloxy)propan-1-al. [0297] Step B: [0298] To a solution of 3-(benzyloxy)propan-1-al (1 g, 6.1 mmol) in THF at 0° C. was added a 1M solution of 4-fluorophenylmagnesium bromide in THF (6.7 mL, 6.7 mmol). The reaction was warmed to room temperature and stirred for 1 h. Work-up and column chromatography by elution with dichloromethane resulted in 0.7 g (44%) of alcohol. [0299] Step C: [0300] To a solution of benzyl ether (500 mg) in ethyl acetate (10 mL) was added 10% Pd(OH)2-C (100 mg). The reaction was stirred under hydrogen gas for 16 h. The reaction mixture was filtered through celite and concentrated. Chromatography of the residue by elution with ethyl acetate-dichloromethane (1:1) resulted in 340 mg (79%) of product.
	In tetrahydrofuran at 0 - 20℃; for 1h;	3.B Step B: To a solution of 3-(benzyloxy)propan-1-al (1 g, 6.1 mmol) in THF at 0° C. was added a 1 M solution of 4-fluorophenylmagnesium bromide in THF (6.7 mL, 6.7 mmol). The reaction was warmed to room temperature and stirred for 1 h. Work-up and column chromatography by elution with dichloromethane resulted in 0.7 g of alcohol.

Reference： [1]Current Patent Assignee: LIGAND PHARMACEUTICALS INC - US2003/229225, 2003, A1 Location in patent: Page 17
[2]Current Patent Assignee: LIGAND PHARMACEUTICALS INC; MERCK & CO INC - US2005/182252, 2005, A1 Location in patent: Page/Page column 37

34
[ 19790-60-4 ]
[ 868525-50-2 ]

Yield	Reaction Conditions	Operation in experiment
88%	Stage #1: 1,1-dibromo-3,3,3-trifluoroacetone With sodium acetate In water for 0.5h; Heating / reflux; Stage #2: 3-Benzyloxypropanal With ammonia; water In methanol at 20℃; for 18h;	1 Preparation 1 : 2-(2-Benzyloxy-ethyl)-5-trifluoromethyl-1 H-imidazole; A mixture of sodium acetate trihydrate (2.7g, 20mmol) and 1 -dibromo-3,3,3-trifluoroacetone (2.7g, 10mmol) in water (18ml_) was heated under reflux for 30 min. The mixture was then cooled to rt and was slowly added to a solution of 4-(phenylmethoxy)propanal (Tetrahedron, 56, 5303- 5310; 2000), (1.48g, 9mmol) and concentrated ammonium hydroxide solution (11ml_) in MeOH (45ml_). The mixture was stirred at rt for 18h and was then evaporated under reduced pressure. The aqueous residue was extracted with EtOAc (3x50mL) and the combined organic solution was dried over magnesium sulfate and concentrated in vacuo to give an oil. The oil was then triturated in water with a trace of MeOH to afford the title compound as a crystalline solid in 88% yield (2.4g). 1H NMR (400MHz, CDCI3) δ: 3.08(t, 2H), 3.80(t, 2H), 4.75(s, 2H), 7.22(d, 1 H), 7.30(m, 5H) LRMS: m/z APCI 271 [M+H]+

Reference： [1]Current Patent Assignee: PFIZER INC - WO2006/72833, 2006, A1 Location in patent: Page/Page column 22

35
[ 19790-60-4 ]
[ 76043-68-0 ]
[ 868525-43-3 ]

Yield	Reaction Conditions	Operation in experiment
38%	With ammonia In acetonitrile at 0 - 20℃; for 48h;	42 4- (Benzyloxy)propanal [(13.37g, 0.08mol), Tetrahedron, 56,5303-5310; 2000) ] was added to an ice-cold solution of preparation 41 (12.4g 0.08mol) in acetonitrile (40mL). 0.88 Ammonia (80mL) was then added portionwise and the mixture was stirred at rt for 48h. The solvent was evaporated under reduced pressure and the residue was partitioned between dichloromethane (400mL) and water (150mL). The aqueous phase was separated and extracted with dichloromethane (250mL) and the combined organic solution was washed with brine (300mL), dried over magnesium sulphate and concentrated in vacuo. The residue was purified by column chromatography on silica gel, eluting with dichloromethane: methanol, 98: 2, to afford the title compound as a viscous orange oil in 38% yield (7.64g).

Reference： [1]Current Patent Assignee: PFIZER INC - WO2005/100322, 2005, A1 Location in patent: Page/Page column 49-50

36
[ 23454-01-5 ]
[ 19790-60-4 ]
[ 868525-08-0 ]

Yield	Reaction Conditions	Operation in experiment
	With ammonia; water In acetonitrile at -5 - 20℃; for 16h;	3 Preparation 3: 2-f2-(Benzvloxv)ethvϖ-4-ethvl-5-ioclo-1 H-imidazole; A solution of 3-benzyloxy-1-propionaldehyde {Tetrahedron, 2000, 56, 5303-5310) (135g, 957mmol) and 2,2-dichlorobutanal {Synthesis, 1975, 455-456) (154.3g, 957mmol) in MeCN (25OmL) was cooled to -50C and treated with 0.88 ammonia (65OmL, added in 5OmL portions). The reaction was then allowed to warm to rt and stirred for 16h. DCM (50OmL) was added to the mixture and the layers separated. The aqueous layer was further extracted with DCM (2 x 20OmL) and the combined organic fraction was washed with brine (50OmL), dried over magnesium sulfate and evaporated under reduced pressure to give 244g of a thick orange oil. This oil was dissolved in DCM (40OmL), cooled to O0C and treated with a solution of sodium hydroxide (46.61g, 1.17mol) in water (20OmL). A slurry of iodine (295.8g, 1.17mol) in methanokdichloromethane (1 :1 , 40OmL) was added and the resulting brown-black mixture was stirred at O0C for 1 h, then allowed to warm to 80C. The mixture was diluted with DCM (40OmL) and treated with 10% aqueous sodium sulphite solution (50OmL) with vigorous stirring. The layers were separated and the aqueous layer further extracted with DCM (2 x 30OmL). The combined organic solution was washed with 10% aqueous sodium sulphite solution (50OmL) and brine (60OmL), dried over magnesium sulfate and concentrated in vacuo. The residue was purified by column chromatography on silica gel, eluting with pentane:ethyl acetate, 50:50 to 0:100, to give a solid. This solid was triturated with pentane to afford the title compound as a white solid in 34% yield (117.44g). LRMS: m/z APCI 357 [M+H] +
	With ammonia In acetonitrile at -5 - 20℃; for 16h;	4; 11a Preparation 4: 2- [2-(Benzyloxy)ethyll-4-ethyl-1 H-imidazole 3-Benzyloxy-1-propionaldehyde (Tetrahedron, 2000,56, 5303-5310) (2.82g, 17.5mmol) was added to a stirred solution of 2,2-dichlorobutanal (Synthesis, 1975, 455-456) (2.47g, 17.5mmol) in acetonitrile (1 OmL) at 0°C under a nitrogen atmosphere, followed by 0.88 ammonia (20mL). The reaction was stirred at rt for 16h. The mixture was evaporated under reduced pressure and the residual liquid was diluted with water (10mL), washed with dichloromethane (3 x 20mL), and the combined organic fraction was dried over magnesium sulphate, filtered and evaporated under reduced pressure. The residue was purified by chromatography on silica gel using an elution gradient of dichloromethane: methanol (100: 0 to 98: 2 to 97: 3). This afforded the title compound as a yellow oil (1.84g). ; Preparation 11: 2-(2-Benzyloxyethyl)-4-ethyl-5-iodo-1 H-i midazole A solution of 3-benzyloxy-1-propionaldehyde (Tetrahedron, 2000, 56, 5303-5310) (135g, 957mmol) and 2,2-dichlorobutanal (Synthesis, 1975,455-456) (154.3g, 957mmol) in acetonitrile (250mL) was cooled to-5°C under a nitrogen atmosphere and treated with 0.88 ammonia (650mL, added in 50mL portions). The reaction was stirred at rt for 16h. Dichloromethane (500mL) was added to the mixture and the layers separated. The aqueous layer was further extracted with dichloromethane (2 x 200mL) and the combined organic fraction was washed with saturated brine (500mL), dried over magnesium sulphate, filtered and evaporated under reduced pressure to give 244g of a thick orange oil. This oil was dissolved in dichloromethane (400mL), cooled to D°C and treated with a solution of sodium hydroxide (46.61g, 1.165mol) in water (200mL). A slurry of iodine (295.8g, 1.165mol) in methanol: dichloromethane (1:1, 400mL) was then added to the well-stirred mixture. The resulting brown-black mixture was stirred for 1 h and allowed to warm to 8°C. The mixture was diluted with d ichloromethane (400mL) and treated with 10% aqueous sodium sulphite solution (500mL) with vigorous mixing. The layers were separated and the aqueous layer further extracted with dichloromethane (2 x 300mL). The combined organic fraction was washed with 10% aqueous sodium sulphite solution (500mL) and saturated brine (600mL), dried over magnesium sulphate, filtered and evaporated under reduced pressure. The residue was purified by chromatography on silica gel using an elution gradient of pentane: ethyl acetate (1: 1 to 0: 1) to give a solid. This solid was treated with pentane (1 L), cooled and stirred; the resulting solid was collected by filtration and washed with pentane (500mL) to afford the title compound as a white solid (117.44g).

Reference： [1]Current Patent Assignee: PFIZER INC - WO2006/72833, 2006, A1 Location in patent: Page/Page column 23
[2]Current Patent Assignee: PFIZER INC - WO2005/100322, 2005, A1 Location in patent: Page/Page column 40-41; 42-43

37
[ 7758-89-6 ]
[ 19790-60-4 ]
[ 622-30-0 ]
[ 2028-63-9 ]
[ 97363-17-2 ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogenchloride; ammonia; In ethanol; hexane; water; ethyl acetate;	Example 1 1-Benzyl-4-(2-benzyloxyethyl)-3-(1-hydroxyethyl)azetidin-2-one To a solution of N-benzylhydroxylamine (3.1g) in ethanol (80ml), under argon, was added 3-benzyloxypropanal (4.45g). The clear solution was stirred for 30 min at ambient temperature and then a solution of butyn-3-ol in water (c 45%, 5ml) was added, followed by copper (I) chloride (3.5g) and concentrated aqueous ammonia (20ml). After stirring at ambient temperature for 2 hrs the mixture was added to hydrochloric acid (2M, 200ml), and then extracted with ethyl acetate (2 x 300ml). The organic extracts were combined and extracted with hydrochloric acid (2M, 100ml) and then saturated aqueous sodium chloride (2 x 100ml). The organic layer was dried over magnesium sulphate and evaporated to dryness. The residue was purified by mplc on silica using a gradient of ethyl acetate/hexane 1:4 changing linearly to ethyl acetate 100%. The appropriate fractions were evaporated to dryness to give 3.7g (44%) of a mixture of cis and trans isomers of the title compound as a clear oil. A sample of the cis isomer isolated as above had the following nmr in CDCl3 at 400 MHz: 1.45 (d, 3H); 1.8 (m, 1H); 2.1 (m, 1H); 3.2 (q, J = 5.5 and 11.0, 1H); 3.3 (m, 1H); 3.55 (m, 1H); 3.6 (m, 1H); 4.1 (m + d, 2H); 4.45, (s, 2H); 4.55 (d, 1H); 7.25 (m, 10H); M + H (FAB)=340.

Reference： [1]Patent: EP223588,1991,B1

38
[ 1629-58-9 ]
[ 19790-60-4 ]
[ 876945-16-3 ]
7-(benzyloxy)-5-hydroxy-4-methylheptan-3-one [ No CAS ]
7-(benzyloxy)-5-hydroxy-4-methylheptan-3-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogen; lithium carbonate In dichloromethane at 0℃; for 24h; Title compound not separated from byproducts.;

Reference： [1]Bee, Cisco; Soo, Bong Han; Hassan, Abbas; Iida, Hiroki; Krische, Michael J. [Journal of the American Chemical Society, 2008, vol. 130, # 9, p. 2746 - 2747]

39
[ 19790-60-4 ]
[ 78-94-4 ]
[ 876944-96-6 ]
6-(benzyloxy)-4-hydroxy-3-methylhexan-2-one [ No CAS ]
6-(benzyloxy)-4-hydroxy-3-methylhexan-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogen; lithium carbonate In dichloromethane at 0℃; for 24h; Title compound not separated from byproducts.;

Reference： [1]Bee, Cisco; Soo, Bong Han; Hassan, Abbas; Iida, Hiroki; Krische, Michael J. [Journal of the American Chemical Society, 2008, vol. 130, # 9, p. 2746 - 2747]

40
[ 19790-60-4 ]
[ 586-96-9 ]
[ 771476-46-1 ]

Yield	Reaction Conditions	Operation in experiment
92%	Stage #1: 3-Benzyloxypropanal; Nitrosobenzene In chloroform at 0℃; for 2h; Stage #2: With sodium tetrahydroborate In ethanol at 0 - 20℃; for 0.333333h; Further stages.;
45%	Stage #1: 3-Benzyloxypropanal; Nitrosobenzene With (2S)-2-{diphenyl[(trimethylsilyl)oxy]methyl}pyrrolidine; 4-nitro-benzoic acid In dichloromethane at -20℃; for 16h; Inert atmosphere; Stage #2: With sodium tetrahydroborate In ethanol; dichloromethane at -20℃; for 0.5h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;
	Stage #1: 3-Benzyloxypropanal; Nitrosobenzene With <i>N</i>-(4,5-dihydro-3<i>H</i>-4-aza-cyclohepta[2,1-<i>a</i>;3,4-<i>a</i>']dinaphthalen-2-yl)-<i>C</i>,<i>C</i>,<i>C</i>-trifluoro-methanesulfonamide In chloroform at 0℃; for 2h; Stage #2: With sodium tetrahydroborate In ethanol; chloroform at 0℃; for 0.25h; optical yield given as %ee; enantioselective reaction;

Multi-step reaction with 2 steps 1: D-Prolin / acetonitrile / 24 h / -20 °C 2: sodium tetrahydroborate / methanol; acetonitrile / 24 h

Reference： [1]Kano, Taichi; Yamamoto, Akihiro; Maruoka, Keiji [Tetrahedron Letters, 2008, vol. 49, # 37, p. 5369 - 5371]
[2]Location in patent: experimental part Mielgo, Antonia; Velilla, Irene; Gomez-Bengoa, Enrique; Palomo, Claudio [Chemistry - A European Journal, 2010, vol. 16, # 25, p. 7496 - 7502]
[3]Location in patent: experimental part Kano, Taichi; Yamamoto, Akihiro; Shirozu, Fumitaka; Maruoka, Keiji [Synthesis, 2009, # 9, p. 1557 - 1563]
[4]Bhosale, Viraj A.; Waghmode, Suresh B. [Tetrahedron, 2017, vol. 73, # 17, p. 2342 - 2348]

41
[ 19790-60-4 ]
[ 99438-28-5 ]
[ 1730-25-2 ]
(R)-1-benzyloxy-hex-5-en-3-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70.2%	Stage #1: (+)-B-methoxydiisocamphenylborane; allylmagnesium bromide In diethyl ether at -78 - 20℃; for 1.25h; Stage #2: 3-Benzyloxypropanal at -78 - 20℃; for 2h; Stage #3: With sodium hydroxide; dihydrogen peroxide In water for 1h; Heating / reflux;

Reference： [1]Current Patent Assignee: UCKUN - US6335364, 2002, B1 Location in patent: Example 3

42
[ 541-16-2 ]
[ 19790-60-4 ]
[ 1072808-18-4 ]

Yield	Reaction Conditions	Operation in experiment
55%	With pyridine; titanium tetrachloride In tetrahydrofuran; tetrachloromethane at 0 - 20℃; Inert atmosphere;

Reference： [1]Liu, Qin; Perreault, Stephane; Rovis, Tomislav [Journal of the American Chemical Society, 2008, vol. 130, # 43, p. 14066 - 14067]

43
[ 591-87-7 ]
[ 19790-60-4 ]
(R)-1-benzyloxy-hex-5-en-3-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
45%	With bis(1,5-cyclooctadiene)diiridium(I) dichloride; caesium carbonate; isopropyl alcohol; 3-nitrobenzoic acid; (R)-(+)-5,5’-dichloro-2,2’-bis(diphenylphosphino)-6,6’-dimethoxy-1,1’-biphenyl In tetrahydrofuran at 120℃; for 20h; Inert atmosphere; optical yield given as %ee;

Reference： [1]Kim, In Su; Ngai, Ming-Yu; Krische, Michael J. [Journal of the American Chemical Society, 2008, vol. 130, # 44, p. 14891 - 14899]

44
[ 100643-27-4 ]
[ 19790-60-4 ]
2-amino-5-benzyloxymethyl-3,7-dihydro-pyrrolo[2,3-<i>d</i>]pyrimidin-4-one [ No CAS ]

Reference： [1]Organic Letters,2009,vol. 11,p. 2465 - 2468

45
[ 19790-60-4 ]
[ 24850-33-7 ]
(S)-1-(benzyloxy)-3-hydroxyhex-5-ene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
100%	Stage #1: 3-Benzyloxypropanal With titanium(IV) isopropylate; (S)-[1,1']-binaphthalenyl-2,2'-diol In dichloromethane for 0.0833333h; Molecular sieve; Inert atmosphere; Reflux; Stage #2: allyltributylstanane In dichloromethane at -78 - -20℃; for 161h; Molecular sieve; Inert atmosphere; Reflux;
86%	With bis(((S)-binaphthoxy)(isopropoxy)titanium) oxide In dichloromethane at -15 - 0℃; for 24h; optical yield given as %ee; enantioselective reaction;
	With bis(((S)-binaphthoxy)(isopropoxy)titanium) oxide In dichloromethane at -20℃; for 72h; Molecular sieve; optical yield given as %ee;

2.57 g

With bis(((S)-binaphthoxy)(isopropoxy)titanium) oxide at -15 - 0℃; for 15h; enantioselective reaction;

A solution of compound 10 (3.00 g, 18.07 mmol) inDCM (40 mL) was added slowly to a suspension of celite(6.00 g) in DCM (30 mL) at room temperature. To this suspensionpyridinium chlorochromate (PCC) (5.76 g, 26.76mmol) was added at 0 °C and the reaction was kept at roomtemperature where the reaction was stirred for 1 h. Celite padfiltration followed by concentration of the filtrate provided aresidue that was purified by column chromatography (1:9).The purified aldehyde (2.82 g, 95%) was directly subjectedto allylation.Ti(OiPr)4 (0.65 g, 2.29 mmol) was added to a solution ofTiCl4 (0.14 g, 0.76 mmol) in DCM (15 mL) at 0 °C under N2environment and the mixture was warmed to room temperatureand stirred for 1.5 h. Silver (I) oxide (0.35 g, 1.52mmol) was then added and the reaction was stirred for 6 hprohibiting direct light. Later DCM (40 mL) followed by (S)-BINOL (0.86 g, 3.05 mmol) were added to reaction mixtureat room temperature and the reaction was allowed to stir for2.5 h to give the chiral bis-Ti(IV) oxide (S, S)-1. The resultingcomplex was cooled to -15 oC to which aldehyde (2.50 g,15.24 mmol) followed by allyltributyltin (6.58 g, 19.81mmol) were added. The reaction was allowed to warm to 0oC and was further stirred for 15 h. The reaction wasquenched by adding saturated aqueous NaHCO3 (50 mL) andthe mixture was extracted with EtOAc (3 30 mL). Thecombined organic layer were separated and dried over anhydrousNa2SO4. Solvent was evaporated under reduced pressureand the crude product was purified by column chromatography (ethyl acetate / hexane, 1: 9) to afford pure (S)-1-(benzyloxy) hex-5-en-3-ol (8) (2.57 g, 82 %, ee 97%) as acolorless liquid. The optical rotation of the compound wasOOOi j OOO OOO3 : 6 (R)3a : 6 (S)4 : 6 (R)4a : 6 (S)1 : 6 (S)1a : 6 (R)Scheme 3. Synthesis of 3, 3a, 4 and 4a.Reagents, conditions and yields: i) CH3COCH=PPh3, C6H6, reflux, 10 h, 80 %, j) PhCH2CH2COCH=PPh3, C6H6, reflux, 14 h, 72 %.O OOBrOPPh3ref 18 g, h17Br+13 1416O15ref 18Scheme 4. Synthesis of 17.Reagents, conditions and yields: g) PPh3, benzene, reflux, 85% 24 h; h) 1 % NaOH, CH2Cl2, r.t., 1 h, 78%.320 Letters in Organic Chemistry, 2013, Vol. 10, No. 5 Shinde et al.[]D32 = - 2.6 (c = 1.0, CHCl3); IR: 3444, 1640, 1492, 1451,1363, 1207 cm-1; 1H NMR (CDCl3, 200 MHz): 7.38-7.22(5H, m), 5.79 (1H, m), 5.11-5.02 (2H, m), 4.50 (2H, s), 3.82(1H, m), 3.73-3.54 (2H, m), 2.71 (1H, brs), 2.21 (2H, t, J =7.0 Hz ), 1.77-1.66 (2H, m); 13C NMR (CDCl3, 50 MHz): 138.1, 135.0, 128.4, 127.9, 127.8, 118.0, 73.5, 70.5, 69.0,42.2, 36.0; ESIMS: m/z 229 [M+Na]+..

Reference： [1]Ochiai, Koji; Kuppusamy, Sankar; Yasui, Yusuke; Harada, Kenji; Gupta, Nishant R.; Takahashi, Yohei; Kubota, Takaaki; Kobayashi, Jun'ichi; Hayashi, Yujiro [Chemistry - A European Journal, 2016, vol. 22, # 10, p. 3287 - 3291]
[2]Location in patent: scheme or table Venkateswar Reddy; Sateesh Chandra Kumar; Suresh Babu; Madhusudana Rao [Tetrahedron Letters, 2009, vol. 50, # 28, p. 4117 - 4120]
[3]Location in patent: scheme or table Reddy, Gandolla Chinna; Balasubramanyam, Penagaluri; Salvanna; Reddy, Thummala Sreenivasulu; Das, Biswanath [Bioorganic and Medicinal Chemistry Letters, 2012, vol. 22, # 7, p. 2415 - 2417]
[4]Shinde, Digambar Balaji; Kanth, Boddu Shashi; Satyakumar, Avula; Kamble; Das, Biswanath [Letters in Organic Chemistry, 2013, vol. 10, # 5, p. 317 - 323]

46
[ 19790-60-4 ]
[ 431-67-4 ]
[ 868525-50-2 ]

Yield	Reaction Conditions	Operation in experiment
88%		A mixture of sodium acetate trihydrate (2.7g, 20mmol) and 1-dibromo-3,3,3- trifluoroacetone (2.7g, 10mmol) in water (18mL) was heated under reflux for 30 min. The mixture was then cooled to rt and was slowly added to a solution of 4- (benzyloxy) propanal (Tetrahedron, 56,5303-5310; 2000) (1.48g, 9mmol) and 0.88 ammonia (11 mL) in methanol (45mL). The mixture was stirred at rt for 18h and was then evaporated under reduced pressure. The aqueous residue was extracted with ethyl acetate (3x50mL) and the combined organic solution was dried over magnesium sulphate and concentrated in vacuo to give an oil. The oil was then triturated in water with a trace of methanol to afford the title compound as a crystalline solid in 88% yield (2.4g).

Reference： [1]Patent: WO2005/100322,2005,A1 .Location in patent: Page/Page column 52

47
[ 506-96-7 ]
[ 19790-60-4 ]
(R)-4-(2-benzyloxyethyl)-oxetane-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
94%	With (2R,6R)-4-benzyl-1,7-bis(trifluoromethylsulfonyl)-2,6-diisopropyl-1,4,7-triazaheptane; dimethylaluminum chloride; N-ethyl-N,N-diisopropylamine In hexane; dichloromethane at -78℃; for 18h; Inert atmosphere;

Reference： [1]Cribiu, Riccardo; Jaeger, Corinna; Nevado, Cristina [Angewandte Chemie - International Edition, 2009, vol. 48, # 46, p. 8780 - 8783]

48
(R)-1-(4-benzyl-2-thioxothiazolidin-3-yl)propan-1-one [ No CAS ]
[ 19790-60-4 ]
[ 1192034-03-9 ]

Yield	Reaction Conditions	Operation in experiment
86%	Stage #1: (R)-1-(4-benzyl-2-thioxothiazolidin-3-yl)propan-1-one With titanium tetrachloride In dichloromethane at 0℃; for 0.166667h; Stage #2: With N-ethyl-N,N-diisopropylamine In 1-methyl-pyrrolidin-2-one; dichloromethane at 0℃; for 1h; Stage #3: 3-Benzyloxypropanal In 1-methyl-pyrrolidin-2-one; dichloromethane at -78 - 0℃; for 3h; diastereoselective reaction;
77%	Stage #1: (R)-1-(4-benzyl-2-thioxothiazolidin-3-yl)propan-1-one With titanium tetrachloride; (-)-sparteine In dichloromethane at -78 - 0℃; Inert atmosphere; Stage #2: 3-Benzyloxypropanal In 1-methyl-pyrrolidin-2-one; dichloromethane at -78 - 0℃; for 3h; Inert atmosphere; diastereoselective reaction;

Reference： [1]Mohapatra, Debendra K.; Reddy, D. Sai; Reddy, G. Sudhakar; Yadav, Jhillu S. [European Journal of Organic Chemistry, 2015, vol. 2015, # 23, p. 5266 - 5274]
[2]Trost, Barry M.; O'Boyle, Brendan M.; Hund, Daniel [Journal of the American Chemical Society, 2009, vol. 131, # 41, p. 15061 - 15074]

49
[ 19790-60-4 ]
[ 56552-80-8 ]

Yield	Reaction Conditions	Operation in experiment
66%	Stage #1: 3-Benzyloxypropanal With Nitrosobenzene; D-Prolin In acetonitrile at -20℃; for 24h; Stage #2: With sodium tetrahydroborate In methanol; acetonitrile for 0.5h; Stage #3: With copper(ll) sulfate pentahydrate In methanol at 0℃; for 10h; enantioselective reaction;
54%	Stage #1: 3-Benzyloxypropanal With Nitrosobenzene; <i>L</i>-proline In acetonitrile at -23 - -20℃; for 24h; Stage #2: With sodium tetrahydroborate In methanol; acetonitrile at 0℃; for 0.333333h; Further stages;
	Multi-step reaction with 3 steps 1: D-Prolin / acetonitrile / 24 h / -20 °C 2: sodium tetrahydroborate / methanol; acetonitrile / 24 h 3: copper(ll) sulfate pentahydrate / methanol / 10 h / 0 °C

Reference： [1]Location in patent: experimental part Sawant, Rajiv T.; Waghmode, Suresh B. [Tetrahedron, 2010, vol. 66, # 11, p. 2010 - 2014]
[2]Location in patent: experimental part Shaikh, Tanveer Mahamadali; Sudalai, Arumugam [Tetrahedron Asymmetry, 2009, vol. 20, # 19, p. 2287 - 2292]
[3]Bhosale, Viraj A.; Waghmode, Suresh B. [Tetrahedron, 2017, vol. 73, # 17, p. 2342 - 2348]

50
[ 1207256-95-8 ]
[ 19790-60-4 ]
(-)-(6-phenylhex-2-ynyloxy)acetic acid 4-(4-phenylbutylidene)tetrahydrofuran-3-yl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
66%	With bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate; hydrogen; (R)-(+)-2,2'-bis(diphenylphosphanyl)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl In dichloromethane at 20℃; optical yield given as %ee; enantioselective reaction;

Reference： [1]Tanaka, Rie; Noguchi, Keiichi; Tanaka, Ken [Journal of the American Chemical Society, 2010, vol. 132, p. 1238 - 1239]

51
[ 674-82-8 ]
[ 67-56-1 ]
[ 19790-60-4 ]
[ 113732-84-6 ]
methyl (2S,3R,6S)-6-(2-benzyloxyethyl)-2-(2-methyl-1,3oxazol-4-yl)-4-oxotetrahydropyran-3-carboxylate [ No CAS ]
[ 1264193-74-9 ]
methyl 6-(2-benzyloxyethyl)-4-hydroxy-2-(2-methyl-1,3-oxazol-4-yl)-5,6-dihydro-2H-pyran-3-carboxylate [ No CAS ]

Reference： [1]Organic Letters,2011,vol. 13,p. 624 - 627

52
[ 19790-60-4 ]
[ 113732-84-6 ]
methyl (2S,3R,6S)-6-(2-benzyloxyethyl)-2-(2-methyl-1,3oxazol-4-yl)-4-oxotetrahydropyran-3-carboxylate [ No CAS ]
[ 1264193-74-9 ]

Reference： [1]Organic Letters,2011,vol. 13,p. 624 - 627

53
[ 19790-60-4 ]
[ 74590-73-1 ]
[ 113732-84-6 ]
2-(2-methyloxazol-4-yl)-6-(2-benzyloxyethyl)-4-oxo-tetrahydro-pyran-3-carboxylic acid methyl ester [ No CAS ]
2-(2-methyloxazol-4-yl)-6-(2-benzyloxyethyl)-4-hydroxy-5,6-dihydro-2H-pyran-3-carboxylic acid methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		General procedure: Neat Ti(Oi-Pr)4 (28 mg, 0.1 mmol) was added to a solution of Binol (29 mg, 0.1 mmol) in THF (10 ml) and stirred for 20 min at rt under a N2 atmosphere. After this time dry LiCl (8 mg, 0.2 mmol) was added and the reaction mixture was stirred for a further 30 min. After this time a solution of aldehyde (5 mmol) in THF (3 ml) was added and the reaction mixture was stirred at rt for 20 min. A solution of Chan?s diene (2.6 g, 10 mmol) in THF (3 ml) was added slowly via a syringe pump at a rate of 30 ml/h. When the addition was complete the reaction mixture was stirred at rt for 12 h. The solvent was removed in vacuo and the residue dissolved in dry MeOH (10 ml), to which was added PPTS (255 mg, 1 mmol) and the mixture was stirred at -12 C for 2 h. After this time the volatiles were removed in vacuo and the residue was dissolved in EtOAc and washed successively with aqueous solutions of saturated NaHCO3 solution and brine. The organics were then dried with MgSO4 and concentrated in vacuo to give a brownish oil.Neat TiCl4 (60 mg, 0.32 mmol) was added to a stirred solution of aldol product (0.3 mmol) and second aldehyde (0.32 mmol) in dry CH2Cl2 (1.5 ml) and the reaction mixture was stirred for 1.5 h. After this time, the reaction mixture was diluted with diethyl ether and the organics washed successively with saturated aqueous sodium bicarbonate solution, brine, dried with MgSO4 and concentrated in vacuo. The residue was purified by flash column chromatography (petroleum ether/EtOAc, 10:1 to 1:1) to yield both trans and cis diastereomers.

Reference： [1]Tetrahedron,2011,vol. 67,p. 4960 - 4966

54
[ 19790-60-4 ]
[ 158070-10-1 ]
rac-(2S,6R)-6-(2-(benzyloxy)ethyl)-2-methyl-3,6-dihydro-2H-pyran [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
95%	Stage #1: 3-Benzyloxypropanal With indium(III) chloride In dichloromethane for 1h; Inert atmosphere; Stage #2: (+/-)-(Z)-5-trimethylsilylpent-4-en-2-ol In dichloromethane at 20℃; for 16h; Inert atmosphere;	4.6. General procedure for the silyl-Prins reaction General procedure: Indium trichloride (1 equiv) was added to a 50 ml round bottom flask containing a carbonyl compound (1 equiv) dissolved in dry DCM (20 ml) under an atmosphere of nitrogen and the resulting solution was stirred for 1 h. After this time the vinylsilyl alcohol (1 equiv) was added and the reaction mixture stirred at room temperature for a further 2-16 h (as indicated by TLC). The reaction mixture was then quenched with distilled water (10 ml) and the water layer was extracted with dichloromethane (40 ml). The combined organic extracts were dried over magnesium sulfate. The solvent was removed in vacuo and the reaction mixture purified by flash column chromatography (normally hexane/diethyl ether 10:1) to give the desired product, usually as an oil.

Reference： [1]Chio, Freda K.; Warne, Julie; Gough, Damien; Penny, Mark; Green, Sasa; Coles, Simon J.; Hursthouse, Mike B.; Jones, Peter; Hassall, Lorraine; McGuire, Thomas M.; Dobbs, Adrian P. [Tetrahedron, 2011, vol. 67, # 27-28, p. 5107 - 5124]

55
[ 1182707-33-0 ]
[ 19790-60-4 ]
[ 1331869-16-9 ]

Yield	Reaction Conditions	Operation in experiment
84%	In tetrahydrofuran; N,N-dimethyl-formamide at -40℃; for 36h; Inert atmosphere;	1 Synthesis of a thioamide compound A-1 Into a heat-vacuum dried 100 mL recovery flask, N,N-dimethylformamide (DMF) (60 mL), 3-(benzyloxy)propanal (1.0 g, 6.09 mmol, 1 equivalent, synthesized according to Amanda M. Heapy, Margaret A. Brimble, Tetrahedron, Vol. 66, No. 29, pp. 5424 to 5431), N,N-diallylthioacetamide (the compound X, 1.13 g, 7.30 mmol, 1.2 equivalents), and the Cu/(S,S)-Ph-BPE solution prepared as above (3.65 mL, 0.365 mmol, 0.06 equivalent) were added under an argon atmosphere. The recovery flask was transferred to a constant temperature bath of -40°C, and the THF solution of 2,2,5,7,8-pentamethylchromanol lithium salt prepared as above (1.83 mL, 0.365 mmol, 0.06 equivalent) was added, followed by stirring at -40°C for 36 hours. Subsequently, a saturated aqueous solution of ammonium chloride (30 mL) and 2,2-bipyridine (57 mg, 0.365 mmol, 0.06 equivalent) were added, and the resulting mixture was extracted three times with ethyl acetate (20 mL). The resulting organic layer was sequentially washed with distilled water, saturated sodium bicarbonate water, and saturated brine, and then dried over anhydrous sodium sulphate. After filtration and concentration, the residue thus obtained was purified by flash column chromatography (hexane/ethyl acetate = 5/1 to 2/1 (volume ratio)) to obtain the following thioamide compound A-1 as a yellow oily matter. Yield 1.64 g (84%, 92%ee).
50%	With (+)-1,2-bis((2S,5S)-2,5-diphenylphospholanyl)ethane; mesitylcopper(I) In N,N-dimethyl-formamide at -60℃; for 60h; Inert atmosphere; Molecular sieve; optical yield given as %ee; enantioselective reaction;

Reference： [1]Current Patent Assignee: MICROBIAL CHEMISTRY RESEARCH FOUNDATION - EP2679580, 2014, A1 Location in patent: Paragraph 0123
[2]Location in patent: scheme or table Kawato, Yuji; Iwata, Mitsutaka; Yazaki, Ryo; Kumagai, Naoya; Shibasaki, Masakatsu [Tetrahedron, 2011, vol. 67, # 35, p. 6539 - 6546]

56
[ 19790-60-4 ]
[ 263764-23-4 ]
(2S,3R)-1-((S)-4-benzyl-2-thioxothiazolidin-3-yl)-5-(benzyloxy)-3-hydroxy-2-methylpentan-1-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
84%	With 1-methyl-pyrrolidin-2-one; titanium(IV) tetrachloride; N-ethyl-N,N-diisopropylamine In dichloromethane at -78 - 0℃;
71%	Stage #1: (S)-1-(4-benzyl-2-thioxothiazolidin-3-yl)propan-1-one With titanium(IV) tetrachloride; N-ethyl-N,N-diisopropylamine In dichloromethane at 0℃; for 0.666667h; Stage #2: With 1-methyl-pyrrolidin-2-one In dichloromethane for 0.25h; Stage #3: 3-Benzyloxypropanal In dichloromethane at -78 - 0℃; for 3h;	(2S,3R)-1-((S)-4-Benzyl-2-thioxothiazolidin-3-yl)-5-(benzyloxy)-3-hydroxy-2-methylpentan-1-one. To a stirred solution of (S)-1-(4-benzyl-2-thioxothiazolidin-3-yl)propan-1-one (1.95 g, 7.36 mmol)and dry DCM (5.0 mL, 1 M) at 0 C was added TiCl4 (0.855 mL, 7.76mmol) dropwise, upon which the mixture turned orange. If necessary,additional DCM (<1 mL) was added to keep the reaction solvated. Afterstirring for 5 min, diisopropylethylamine (1.42 mL, 8.1 mmol) wasadded dropwise. The dark purple reaction mixture was allowed to stirfor an additional 40 min at 0 C, and after N-methylpyrrolidone (1.42mL, 14.73 mmol) was added dropwise, the reaction was stirred for 15min. Next the mixture was cooled to 78 C and 3-(benzyloxy)propanal(0.81 g, 4.91 mmol) in 0.5 mL DCM was added dropwise. The reactionwas stirred at 78 C for 2 h, and then warmed to 0 C and stirred for 1h. After complete consumption of the aldehyde, the reaction mixturewas quenched with saturated NH4Cl. The aqueous layer was extractedwith DCM (3×), and the combined organic layers were washed withbrine, dried over Na2SO4, filtered, and concentrated under reducedpressure. The crude product was purified by silica gel flash columnchromatography (0 to 20% EtOAc in hexanes) to give the syn aldolproduct as a yellow oil (1.5 g, 71%). The spectral data was consistentwith reported values [47]. [α]22D + 135 (c = 1.00, CHCl3) 1H NMR (400Hz, 1H), 4.45 (s, 2H), 4.10 (dp, J = 10.2, 4.1, 3.5 Hz, 1H), 3.71-3.48 (m,2H), 3.32 (dd, J = 11.6, 7.1 Hz, 1H), 3.23 (s, J = 2.3 Hz, 1H), 3.18 (dd, J= 13.2, 3.8 Hz, 1H), 2.98 (dd, J = 13.2, 10.6 Hz, 1H), 2.82 (d, J = 11.5Hz, 1H), 1.87-1.58 (m, 2H), 1.21 (d, J = 6.8 Hz, 3H). 13C NMR (100MHz, CDCl3) δ 201.5, 177.8, 138.0, 136.6, 129.6 (2C), 129.0 (2C), 128.6(2C), 127.9 (2C), 127.4 (2C), 73.5, 71.8, 69.2, 68.8, 43.9, 36.8, 34.0,32.3, 11.1. HRMS calc’d for C23H27NO3S2 (M+Na)+ 452.5822, found(M+Na)+ 452.1318.
71%	Stage #1: (S)-1-(4-benzyl-2-thioxothiazolidin-3-yl)propan-1-one With titanium(IV) tetrachloride; N-ethyl-N,N-diisopropylamine In dichloromethane at 0℃; for 0.666667h; Stage #2: With 1-methyl-pyrrolidin-2-one In dichloromethane for 0.25h; Stage #3: 3-Benzyloxypropanal In dichloromethane at -78 - 0℃; for 3h;	(2S,3R)-1-((S)-4-Benzyl-2-thioxothiazolidin-3-yl)-5-(benzyloxy)-3-hydroxy-2-methylpentan-1-one. To a stirred solution of (S)-1-(4-benzyl-2-thioxothiazolidin-3-yl)propan-1-one (1.95 g, 7.36 mmol)and dry DCM (5.0 mL, 1 M) at 0 C was added TiCl4 (0.855 mL, 7.76mmol) dropwise, upon which the mixture turned orange. If necessary,additional DCM (<1 mL) was added to keep the reaction solvated. Afterstirring for 5 min, diisopropylethylamine (1.42 mL, 8.1 mmol) wasadded dropwise. The dark purple reaction mixture was allowed to stirfor an additional 40 min at 0 C, and after N-methylpyrrolidone (1.42mL, 14.73 mmol) was added dropwise, the reaction was stirred for 15min. Next the mixture was cooled to 78 C and 3-(benzyloxy)propanal(0.81 g, 4.91 mmol) in 0.5 mL DCM was added dropwise. The reactionwas stirred at 78 C for 2 h, and then warmed to 0 C and stirred for 1h. After complete consumption of the aldehyde, the reaction mixturewas quenched with saturated NH4Cl. The aqueous layer was extractedwith DCM (3×), and the combined organic layers were washed withbrine, dried over Na2SO4, filtered, and concentrated under reducedpressure. The crude product was purified by silica gel flash columnchromatography (0 to 20% EtOAc in hexanes) to give the syn aldolproduct as a yellow oil (1.5 g, 71%). The spectral data was consistentwith reported values [47]. [α]22D + 135 (c = 1.00, CHCl3) 1H NMR (400Hz, 1H), 4.45 (s, 2H), 4.10 (dp, J = 10.2, 4.1, 3.5 Hz, 1H), 3.71-3.48 (m,2H), 3.32 (dd, J = 11.6, 7.1 Hz, 1H), 3.23 (s, J = 2.3 Hz, 1H), 3.18 (dd, J= 13.2, 3.8 Hz, 1H), 2.98 (dd, J = 13.2, 10.6 Hz, 1H), 2.82 (d, J = 11.5Hz, 1H), 1.87-1.58 (m, 2H), 1.21 (d, J = 6.8 Hz, 3H). 13C NMR (100MHz, CDCl3) δ 201.5, 177.8, 138.0, 136.6, 129.6 (2C), 129.0 (2C), 128.6(2C), 127.9 (2C), 127.4 (2C), 73.5, 71.8, 69.2, 68.8, 43.9, 36.8, 34.0,32.3, 11.1. HRMS calc’d for C23H27NO3S2 (M+Na)+ 452.5822, found(M+Na)+ 452.1318.

Reference： [1]Dechert-Schmitt, Anne-Marie R.; Schmitt, Daniel C.; Krische, Michael J. [Angewandte Chemie - International Edition, 2013, vol. 52, # 11, p. 3195 - 3198][Angew. Chem., 2013, vol. 125, # 11, p. 3277 - 3280,4]
[2]Coulup, Sara K.; Georg, Gunda I.; Henry; Huang, David S.; Noman, Md Abdullah Al; Syeda, Shameem Sultana; Wong, L. [Bioorganic Chemistry, 2022, vol. 125]
[3]Coulup, Sara K.; Georg, Gunda I.; Henry; Huang, David S.; Noman, Md Abdullah Al; Syeda, Shameem Sultana; Wong, L. [Bioorganic Chemistry, 2022, vol. 125]

57
[ 1426942-85-9 ]
[ 19790-60-4 ]
[ 1440543-49-6 ]

Yield	Reaction Conditions	Operation in experiment
69%	Stage #1: 6-chloro-2-(4-fluoroindolin-2-yl)pyridin-3-ol; 3-Benzyloxypropanal With trifluoroacetic acid In acetonitrile at 20℃; for 3h; Stage #2: With sodium hydrogencarbonate In water; acetonitrile	31.1 Step 1 - Synthesis of 6-(2-(benzyloxy)ethyl)-2-chloro-l l-fluoro-12, 12a-dihydro-6H- pyrido[ 2 ', 3 ':5, 6][ 1, 3 Joxazinof 3, 4-a] indole To a solution of 3-(benzyloxy)propanal (465 mg, 2.83 mmol) and 6-chloro-2-(4- fluoroindolin-2-yl)pyridin-3-ol (500 mg, 1.89 mmol) in MeCN (15 mL) was added TFA (10 mg, 0.09 mmol). The mixture was stirred at room temperature for 3 hours. The it was basified by NaHC03 (aq.), and then it was concentrated in vacuo, the resulting residue was purified using column chromatography (petroleum ether : EtOAc = 10 : 1) to provide 6-(2-(benzyloxy)ethyl)-2- chloro-1 l-fluoro-12, 12a-dihydro-6H-pyrido[2',3':5,6][l,3]oxazino[3,4-a]indole (540 mg, yield: 69%). 1H- MR (CDCI3, 400 MHz) δ 7.28-7.38 (m, 5H), 7.04-7.10 (m, 2H), 6.95 (d, J= 8.8 1H), 6.60 (d, J= 8.0 Hz, 1H), 6.50 (t, J= 8.0 Hz, 1H), 5.93 (t, J= 7.2 Hz, 1H), 5.02 (d, J= S.i Hz, 1H), 4.55 (d, J= 2.4 Hz, 1H), 3.62-3.71 (m, 3H), 3.40-3.48 (m, 1H), 2.19-2.27 (m, 2H). MS (M+H)+: 411.
69%	With trifluoroacetic acid In acetonitrile at 20℃; for 3h;	31.1 Step 1-Synthesis of 6-(2-(benzyloxy)ethyl)-2-chloro-11-fluoro-12,12a-dihydro-6H-pyrido[2',3':5,6][1,3]oxazino[3,4-a]indole Step 1-Synthesis of 6-(2-(benzyloxy)ethyl)-2-chloro-11-fluoro-12,12a-dihydro-6H-pyrido[2',3':5,6][1,3]oxazino[3,4-a]indole To a solution of 3-(benzyloxy)propanal (465 mg, 2.83 mmol) and 6-chloro-2-(4-fluoroindolin-2-yl)pyridin-3-ol (500 mg, 1.89 mmol) in MeCN (15 mL) was added TFA (10 mg, 0.09 mmol). The mixture was stirred at room temperature for 3 hours. The it was basified by NaHCO3 (aq.), and then it was concentrated in vacuo, the resulting residue was purified using column chromatography (petroleum ether:EtOAc=10:1) to provide 6-(2-(benzyloxy)ethyl)-2-chloro-11-fluoro-12,12a-dihydro-6H-pyrido[2',3':5,6][1,3]oxazino[3,4-a]indole (540 mg, yield: 69%). 1H-NMR (CDCl3, 400 MHz) δ 7.28˜7.38 (m, 5H), 7.04˜7.10 (m, 2H), 6.95 (d, J=8.8 Hz, 1H), 6.60 (d, J=8.0 Hz, 1H), 6.50 (t, J=8.0 Hz, 1H), 5.93 (t, J=7.2 Hz, 1H), 5.02 (d, J=8.8 Hz, 1H), 4.55 (d, J=2.4 Hz, 1H), 3.62˜3.71 (m, 3H), 3.40˜3.48 (m, 1H), 2.19˜2.27 (m, 2H). MS (M+H)+: 411.

Reference： [1]Current Patent Assignee: WUXI APPTEC CO., LTD. - WO2013/33971, 2013, A1 Location in patent: Page/Page column 106; 107
[2]Current Patent Assignee: WUXI APPTEC CO., LTD. - US2014/213571, 2014, A1 Location in patent: Paragraph 0453

58
[ 70303-51-4 ]
[ 19790-60-4 ]
C₂₁H₃₈O₂Si₂ [ No CAS ]
[ 1446785-83-6 ]

Yield	Reaction Conditions	Operation in experiment
1: 44 mg 2: 36%	With boron trifluoride diethyl etherate In dichloromethane at -78℃; for 19h; Molecular sieve; diastereoselective reaction;	Typical experimental procedure for the preparation of 3 To a stirred solution ofsilane 2a (56 mg, 280 lmol), BF3OEt2 (35 lL, 280 lmol) and 4 Å molecularsieves (100 mg/mL solvent) in CH2Cl2 (1 mL) at 78 C was added a 0.01 Msolution of aldehyde 1a (29 mg, 140 lmol) and 1-methylnaphthalene (25 mg,140 lmol) in CH2Cl2 (1 mL) dropwise over 1 h, and the resultant mixture wasstirred overnight. The reaction was quenched by the addition of NH4Cl (1 mL).The aqueous phase was extracted (CH2Cl2, 3 5 mL), and the combined organicphases were washed (H2O, 2 10 mL), dried (MgSO4) and concentrated underreduced pressure. The residue was purified by flash chromatography(pentaneCH2Cl2) to give 3a (44 mg, 120 lmol) as a colorless oil in 86% yield.1H NMR (500 MHz, CDCl3) d 7.34-7.33 (m, 4H), 7.29-7.26 (m, 1H), 4.51 (s, 2H),3.90 (q, J = 6.5 Hz, 1H), 3.84-3.79 (m, 1H), 3.67-3.63 (m, 1H), 3.57-3.52 (m,1H), 1.94 (dd, J = 13.4, 6.9 Hz, 2H), 1.27 (d, J = 5.9 Hz, 3H), 1.24-1.21 (m, 1H),0.89 (dd, J = 8.4, 5.0 Hz, 1H), 0.05 (s, 9H), 0.02 (s, 9H); 13C NMR (500 MHz,CDCl3) d 138.6, 128.3, 127.7, 127.5, 79.4, 76.8, 73.1, 69.0, 34.9, 33.9, 33.6, 22.3,0.6, 2.4.

Reference： [1]Borg, Tessie; Timmer, Brian; Somfai, Peter [Tetrahedron Letters, 2013, vol. 54, # 30, p. 3916 - 3918]

59
[ 19790-60-4 ]
[ 263764-23-4 ]
[ 1464823-37-7 ]

Yield	Reaction Conditions	Operation in experiment
90%	With titanium tetrachloride; N-ethyl-N,N-diisopropylamine In dichloromethane at -20℃; diastereoselective reaction;
85%	Stage #1: (S)-3-propanoyl-4-benzyl-1,3-thiazolidine-2-thione With titanium tetrachloride In dichloromethane at -78℃; for 0.5h; Inert atmosphere; Stage #2: With N-ethyl-N,N-diisopropylamine In dichloromethane at -78℃; for 1h; Inert atmosphere; Stage #3: 3-Benzyloxypropanal In dichloromethane at -78℃; for 2h; Inert atmosphere;	1 (2R,3S)-1-((S)-4-Benzyl-2-thioxothiazolidin-3-yl)-5-(benzyloxy)-3-hydroxy-2-methylpentan-1-one 9 4.1.1 (2R,3S)-1-((S)-4-Benzyl-2-thioxothiazolidin-3-yl)-5-(benzyloxy)-3-hydroxy-2-methylpentan-1-one 9 To a stirred solution of auxillary 8 7 (12.0 g, 45.7 mmol) in dry CH2Cl2 (50 mL) cooled to -78 °C, was added 2 M TiCl4 in CH2Cl2 (16 mL, 30.12 mmol) at the same temperature under an N2 atmosphere. The reaction mixture was stirred for 30 min. To this was added DIPEA (5.2 mL, 30.12 mmol) and allowed to stir for 1 h at the same temperature. Next, benzyl protected propanaldehyde 7 (5.0 g, 30.12 mmol) dissolved in CH2Cl2 (20 mL) was added to it and the mixture was allowed to stir for 2 h at -78 °C. The reaction was monitored by the TLC. After completion of the reaction, it was quenched with 50% NH4Cl (10 mL) and extracted with CH2Cl2 (2 * 15 mL). The organic layer was washed with water, brine, dried over anhydrous Na2SO4 and evaporated in vacuo. The crude residue was chromatographed over silica gel (20% EtOAc/petroleum ether) to afford yellow coloured 9 (10.2 g, 85% yield, 95% de). (c 0.44, CHCl3). 1H NMR (300 MHz, CDCl3): δH 7.38-7.24 (m, 10H), 5.41-5.35 (m, 1H), 4.76-4.69 (m, 1H), 4.52 (s, 2H), 4.27 (d, J = 9.95 Hz, 1H), 3.73-3.59 (m, 2H), 3.35 (dd, J = 7.24, 10.86 Hz, 1H), 3.22 (dd, J = 3.62, 12.67 Hz, 1H), 3.05-2.97 (m, 1H), 2.87 (d, J = 10.86 Hz, 1H), 1.92-1.81 (m, 1H), 1.78-1.70 (m, 1H), 1.53 (br s, 1H), 1.22 (d, J = 7.24 Hz, 3H). 13C NMR (75 MHz, CDCl3): δC = 201.3, 177.5, 138.0, 136.3, 129.3, 128.3, 127.65, 127.61, 127.1, 73.2, 69.9, 68.8, 68.3, 43.1, 36.9, 33.6, 31.7, 11.2. IR (neat) νmax: 3485, 2922, 2854, 1645, 1294, 743 cm-1; MS (ESI): m/z = 452.1 [M+H]+; HRMS (ESI): calcd for C23H27NO3S2Na: 452.1325; found: 452.1290 [M+Na]+.

Reference： [1]Yadav, Jhillu Singh; Gyanchander, Eppa; Mishra, Anand Kumar; Adithya, Peddapuram; Das, Saibal [Tetrahedron Letters, 2013, vol. 54, # 44, p. 5879 - 5882]
[2]Chandrasekhar, Srivari; Sathish, Kurapati; Reddy, Gangireddy Pavan Kumar; Mainkar, Prathama S. [Tetrahedron Asymmetry, 2014, vol. 25, # 4, p. 348 - 355]

60
[ 631-67-4 ]
[ 19790-60-4 ]
C₁₄H₂₁NO₂S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
24%	In tetrahydrofuran; N,N-dimethyl-formamide at -40℃; for 40h; Inert atmosphere;	4 Synthesis of a thioamide compound A-2 Into a heat-vacuum dried 20 mL recovery flask, DMF (2 mL), 3-(benzyloxy)propanal (33 µL, 0.20 mmol, 1 equivalent, synthesized according to Amanda M. Heapy, Margaret A. Brimble, Tetrahedron, Vol. 66, No. 29, pp. 5424 to 5431), N,N-dimethylthioacetamide (manufactured by Alfa Aesar, 24.5 g, 0.24 mmol, 1.2 equivalents), and the Cu/(S,S)-Ph-BPE solution prepared as above (120 µL, 0.012 mmol, 0.06 equivalent) was added under an argon atmosphere. The recovery flask was transferred to a constant temperature bath of -40°C, and the THF solution of 2,2,5,7,8-pentamethylchromanol lithium salt prepared as above (60 µL, 0.012 mmol, 0.06 equivalent) was added, followed by stirring at -40°C for 40 hours. Subsequently, a saturated aqueous solution of ammonium chloride (2 mL) and 2,2-bipyridine (1.8 mg, 0.012 mmol, 0.06 equivalent) were added, and the resulting mixture was extracted three times with ethyl acetate (3 mL). The resulting organic layer was sequentially washed with distilled water, saturated sodium bicarbonate water, and saturated brine, and then dried over anhydrous sodium sulphate. After filtration and concentration, the residue thus obtained was purified by flash column chromatography (hexane/ethyl acetate = 5/1 to 1/1 (volume ratio)) to obtain the following thioamide compound A-2 as a yellow oily matter. Yield 12.8 mg (24%, 90%ee).

Reference： [1]Current Patent Assignee: MICROBIAL CHEMISTRY RESEARCH FOUNDATION - EP2679580, 2014, A1 Location in patent: Paragraph 0130

61
(1E)-3-(tert-butyldimethylsilyloxy)-1-dimethylamino-1,3-pentadiene [ No CAS ]
[ 19790-60-4 ]
[ 762-42-5 ]
[ 1548658-78-1 ]
(2R*,3S*)-2-(2-benzyloxyethyl)-3-methyl-2,3-dihydro-4H-pyran-4-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	Stage #1: (1E)-3-(tert-butyldimethylsilyloxy)-1-dimethylamino-1,3-pentadiene; 3-Benzyloxypropanal With C₆₈H₅₂N₈O₁₂Rh₂*3H₂O In dichloromethane at -20℃; for 6h; Inert atmosphere; Stage #2: dimethyl acetylenedicarboxylate In dichloromethane at 0℃; for 0.166667h; Inert atmosphere; Stage #3: With acetyl chloride In dichloromethane at -78℃; for 0.5h; Inert atmosphere; stereoselective reaction;	5.1 4.5.1. (2R,3S)-3-Methyl-2-(2-phenylethyl)-2,3-dihydro-4H-pyran-4-one 5c General procedure: A solution of diene 8b (109 mg, 0.45 mmol, Z/E = 74:26) in CH2Cl2 (0.3 mL) was added to a solution of hydrocinnamaldehyde 4c (40.2 mg, 0.30 mmol) and Rh2((S)-BPTPI)4·3H2O 2 (12.9 mg, 0.009 mmol, 3 mol %) in CH2Cl2 (0.3 mL) at -20 °C. After stirring at this temperature for 6 h, a solution of dimethyl acetylenedicarboxylate (DMAD) (42.6 mg, 0.3 mmol) in CH2Cl2 (0.6 mL) was added and the mixture was stirred at 0 °C for 10 min. The whole mixture was cooled to -78 °C and treated dropwise with a 1 M solution of AcCl in CH2Cl2 (0.60 mL, 0.60 mmol). After stirring for ca. 30 min, the reaction was quenched with saturated NaHCO3 (3 mL) and extracted with EtOAc (2 × 10 mL). The combined organic layers were washed with water (3 mL) and brine (2 × 3 mL), and dried over anhydrous Na2SO4. Filtration and evaporation in vacuo furnished the crude product, which was purified by column chromatography (silica gel 5 g, 9:1 hexane/EtOAc) to provide 5c (42.1 mg, 97%) as a colorless oil and 15 (39.6 mg, 26% based on 8b) as a colorless oil.

Reference： [1]Watanabe, Yudai; Shimada, Naoyuki; Anada, Masahiro; Hashimoto, Shunichi [Tetrahedron Asymmetry, 2014, vol. 25, # 1, p. 63 - 73]

62
[ 124-38-9 ]
[ 19790-60-4 ]
[ 1774-47-6 ]
[ 171110-94-4 ]

Yield	Reaction Conditions	Operation in experiment
80%	Stage #1: trimethylsulfoxonium iodide With sodium hydride In dimethyl sulfoxide at 25℃; for 0.0833333h; Inert atmosphere; Stage #2: 3-Benzyloxypropanal In tetrahydrofuran; dimethyl sulfoxide for 1h; Inert atmosphere; Stage #3: carbon dioxide In tetrahydrofuran; dimethyl sulfoxide at 40℃; for 6h; Inert atmosphere;	General Experimental Procedure for the Preparation ofCyclic Carbonates 4a-v General procedure: NaH (0.132 g, 3.3 mmol; previously washed with anhydrousPE to remove oil) was taken in an oven-dried three-neckedflask, followed by addition of anhydrous DMSO (10 mL)through a septum to it, and the whole slurry was stirred at 25°C under N2 atmosphere. Solid Me3SOI (0.726 g, 3.3 mmol)was added to the slurry with stirring over a period of 5 minvia a solid addition funnel until it becomes a homogeneoussolution. A solution of aldehyde 1a-v (3 mmol), dissolved inanhydrous THF (10 mL), was added dropwise to the reactionmixture. After 1 h, CO2 (1 atm) was then bubbled slowly viaa needle into the reaction mixture, (after ascertaining thataldehyde was completely converted into epoxide, monitoredby TLC) at 40 °C, for 6 h. Water (10 mL) was added toquench the reaction. It was then extracted with EtOAc (3 ×20 mL); the organic layer was washed with brine and driedover anhydrous Na2SO4 and the solvent concentrated,product purified by silica gel column chromatography (100-200 mesh) using PE and EtOAc (70:30) as eluent to affordpure cyclic carbonates 4a-v.

Reference： [1]Aher, Ravindra D.; Kumar, B. Senthil; Sudalai, Arumugam [Synlett, 2014, vol. 25, # 1, p. 97 - 101]

63
[ 19790-60-4 ]
(Z)-6-(phenyl)hex-3-en-1-ol [ No CAS ]
C₂₂H₂₆O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%	With iron(III) chloride In dichloromethane at 23℃; Inert atmosphere; Molecular sieve; diastereoselective reaction;	Prins-Friedel Crafts Experimental Conditions with Primary Alkenols General procedure: To a flame dried roundbottom flask, 140 mg of 4Å molecular sieves were added and further flame dried under reducedpressure for 15 minutes. In a separate flask, alkenol (0.284 mmol, 1.0 eq), aldehyde (0.340mmol, 1.2 eq), and methylene chloride (2.8 mL, 0.1M) were combined and were cannulated tothe flask containing molecular sieves. In one addition, 10 mol % FeCl3 was added and monitoredby TLC. Upon completion, the reaction was quenched by passing through a plug of silica gel andconcentrated. Diastereoselectivities were determined by crude 1H NMR and eventually purifiedby column chromatography (1:9 EtOAc:Hex) to afford the pure polycyclic rings.

Reference： [1]Ghosh, Arun K.; Keyes, Chad; Veitschegger, Anne M. [Tetrahedron Letters, 2014, vol. 55, # 30, p. 4251 - 4254]

64
(E)-6-(phenyl)hex-3-en-1-ol [ No CAS ]
[ 19790-60-4 ]
C₂₂H₂₆O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
77%	With iron(III) chloride In dichloromethane at 23℃; Inert atmosphere; Molecular sieve; diastereoselective reaction;	Prins-Friedel Crafts Experimental Conditions with Primary Alkenols General procedure: To a flame dried roundbottom flask, 140 mg of 4Å molecular sieves were added and further flame dried under reducedpressure for 15 minutes. In a separate flask, alkenol (0.284 mmol, 1.0 eq), aldehyde (0.340mmol, 1.2 eq), and methylene chloride (2.8 mL, 0.1M) were combined and were cannulated tothe flask containing molecular sieves. In one addition, 10 mol % FeCl3 was added and monitoredby TLC. Upon completion, the reaction was quenched by passing through a plug of silica gel andconcentrated. Diastereoselectivities were determined by crude 1H NMR and eventually purifiedby column chromatography (1:9 EtOAc:Hex) to afford the pure polycyclic rings.

Reference： [1]Ghosh, Arun K.; Keyes, Chad; Veitschegger, Anne M. [Tetrahedron Letters, 2014, vol. 55, # 30, p. 4251 - 4254]

65
[ 14593-43-2 ]
[ 22539-93-1 ]
[ 19790-60-4 ]

Reference： [1]ChemCatChem,2015,vol. 7,p. 2318 - 2322

66
[ 19790-60-4 ]
[ 530-47-2 ]
(E)-2-(3-(benzyloxy)propylidene)-1,1-diphenylhydrazine [ No CAS ]

Reference： [1]Advanced Synthesis and Catalysis,2015,vol. 357,p. 2939 - 2943

67
[ 1375257-24-1 ]
[ 19790-60-4 ]
(S)-3-[(R)-5 (benzyloxy)-3-hydroxypentanoyl]-4-isopropyl-1-[(R)-1-phenylethyl]imidazolidin-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87%	Stage #1: N-acetyl-(S)-4-isopropyl-1-[(R)-1-phenylethyl] imidazolidin-2-one With lithium hexamethyldisilazane In tetrahydrofuran at -78℃; for 1h; Inert atmosphere; Stage #2: 3-Benzyloxypropanal for 1h; Inert atmosphere; diastereoselective reaction;	Synthesis of (S)-3-((R)-5-(benzyloxy)-3-hydroxypentanoyl)-4-isopropyl-1-((R)-1-phenylethyl) imidazolidin-2-one (9) To asolution of N-acetylated chiral auxiliary(7) (10 g, 36.4 mmol, 1.0 equiv.) in anhydrous THF (50 mL) under nitrogen atmospherewas added LiHMDS solution (40.1 mL, 1.1 equiv; 1.0 M in THF) at -78 oC, and stirred for 1h. 3-(Benzyloxy)propanal(8) (5.9 g, 36.4 mmol, 1.0 equiv.) was then added tothe reaction mixture and allowed to stir for another 1h. Progress of thereaction was monitored by TLC. After completion of reaction, the reactionmixture was quenched with saturated aq. NH4Cl solution, extractedwith EtOAc and further washed with brine. The organic layer was dried overanhydrous sodium sulfate, concentrated under reduced pressure to afford thecrude product which was further purified by column chromatography on silica gel(60-120 mesh) using petroleum ether/EtOAc (8:2) as eluent to afford the desired product.Colourlessliquid; Yield 87% (14.0 g); [α]D20 +56.5 (c = 1, CHCl3); 1HNMR (400 MHz, CDCl3): δ 0.82 (d, J= 6.9 Hz, 3H), 0.89 (d, J = 7.0 Hz,3H), 1.59 (d, J = 7.2 Hz, 3H),1.85-1.90 (m, 2H), 2.39-2.43 (m, 1H), 2.92-3.29 (m, 4H), 3.66-3.74(m, 3H),4.20-4.24 (m, 2H), 4.54 (s, 2H), 5.35 (q, J= 7.0 Hz, 1H), 7.27-7.39 (m, 10H); 13C NMR (100 MHz, CDCl3):δ 14.5, 16.1, 18.1, 28.7, 36.6, 37.2, 42.8, 50.4, 55.2, 66.5, 67.5, 73.1,127.2, 127.5, 127.7, 128.0, 128.4, 128.8, 138.4, 138.9, 154.6, 172.8; HRMS(ESI-TOF) m/z: calc’d for C26H34N2NaO4([M+Na]+):461.2411, found: 461.2416.

Reference： [1]Goyal, Sandeep; Patel, Bhautikkumar; Sharma, Ratnesh; Chouhan, Mangilal; Kumar, Kapil; Gangar, Mukesh; Nair, Vipin A. [Tetrahedron Letters, 2015, vol. 56, # 40, p. 5409 - 5412]

68
[ 534-22-5 ]
[ 19790-60-4 ]
3-(benzyloxy)-1-(5-methylfuran-2-yl)propan-1-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78%	Stage #1: 2-methylfuran With n-butyllithium In tetrahydrofuran; hexane at -78 - -5℃; for 2h; Inert atmosphere; Stage #2: 3-Benzyloxypropanal In tetrahydrofuran; hexane at -78 - 20℃; for 15h; Inert atmosphere;	3-(benzyloxy)-1-(5-methylfuran-2-yl)propan-1-ol The general procedure for the preparation of alkylfurans was employed with dry THF(25 mL), 3-(benzyloxy)propanal (1.9 g, 11.58 mmol in 5 mL of THF), 2-methylfuran (1.15 mL, 12.74 mmol), n-BuLi (1.6M, 9.4 mL, 15.05 mmol, 2.5 Min hexanes). The reaction completed for 15 h. Purification by silica gel column chromatography afforded 20 (1.15 g,78%, Rf=0.33,EtOAc/hexanes, 1:5) as a light yellow liquid. 1HNMR (400 MHz, CDCl3)δ 7.39-7.25 (m, 5H), 6.11 (d, J=3.0,1H), 5.89 (m, 1H), 4.87 (dt, J=8.3, J=4.3, 1H), 4.56-4.50 (m, 2H), 3.72(ddd, J=9.5, J=6.7, J=4.9, 1H), 3.65(ddd, J=9.5, J=6.7, J=4.9, 1H), 3.09(m, 1H), 2.28 (s, 3H), 2.23-2.06 (m, 2H); 13CNMR (100 MHz, CDCl3)δ 154.8, 151.8, 138.2, 128.7, 128.0, 127.9, 106.8, 106.2, 73.5, 68.3, 66.9,35.3, 13.8; IR (neat, cm-1) 3413, 3064, 3031, 2919, 2862, 2001,2484, 1725, 1631, 1552, 1294, 1227, 1171, 1070.

Reference： [1]Kazancioglu, Mustafa Zahrittin; Akin Kazancioglu, Elif; Secen, Hasan; Altundas, Ramazan [Tetrahedron Letters, 2015, vol. 56, # 50, p. 6994 - 6997]

69
[ 625-31-0 ]
[ 19790-60-4 ]
rac-(2S,6R)-6-(2-(benzyloxy)ethyl)-2-methyl-3,6-dihydro-2H-pyran [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
41%	Stage #1: Pent-4-en-2-ol; 3-Benzyloxypropanal With trimethylsilyl bromide; lithium iodide In 1,2-dichloro-ethane at 0℃; for 0.666667h; Inert atmosphere; Stage #2: With indium(III) acetate for 3h; Inert atmosphere; Reflux;	4.4 General procedure C for the one-pot synthesis of dihydropyrans General procedure: To a solution of aldehyde 6 (1mmol, 1equiv) in dichloroethane (10mL) was added but-4-en-2-ol 5 (1.6equiv), and lithium iodide (2equiv) under argon. TMSBr (1equiv) was added at 0°C followed 40min later by addition of the Lewis acid In(OAc)3 (2equiv). The mixture was refluxed for 3h. It was cooled to room temperature, filtered on Celite and rinsed with dichloromethane. The organic layers were washed with a saturated aqueous solution of Na2S2O3, then a saturated aqueous solution of NaHCO3 and brine and finally dried over anhydrous MgSO4. They were filtered, and concentrated under reduced pressure to give a crude complex mixture. The expected DHP (±)-10 was purified by column chromatography on silica gel.

Reference： [1]Chalopin, Thibaut; Jebali, Khaoula; Gaulon-Nourry, Catherine; Dénès, Fabrice; Lebreton, Jacques; Mathé-Allainmat, Monique [Tetrahedron, 2016, vol. 72, # 2, p. 318 - 327]

70
[ 19790-60-4 ]
((3,3-difluoropropoxy)methyl)benzene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With diethylamino-sulfur trifluoride In dichloromethane at 20℃;
71%	With diethylamino-sulfur trifluoride In dichloromethane at 0 - 20℃; for 16h;
	With diethylamino-sulfur trifluoride In dichloromethane at 15℃; for 16h;	153.2 [0367] Step 2: ((3,3-Difluoropropoxy)methyl)benzene [0368] 3-l3enzyloxypropanal (From step 1, 6.0 g, 36.54 mmol) in dichioromethane (60 mE) was added diethylaminosulthr trifluoride (9.66 mE, 3.08 mmol) at 0 dropwise. The resulting mixture was stirred at 15° C. for 16 hours. The solution was quenched with saturated aqueous NaHCO3 solution (300 mE) and the mixture was extracted with dichloromethane (300 mEx2). The combined organic layers were dried over anhydrous Na2504 and concentrated to dryness. The residue was purified by column chromatography (0-10% EtOAc in petroleum ether) to afford the title compound (4.8 g, yield 71%) as a light yellow oil (1.8 g pure and 3.0 g of 80% purity). ‘H NMR (400 MHz, CDC13) ö 7.38-7.30 (m, 5H), 6.16-5.85 (m, 1H), 4.52 (s, 2H), 3.63 (t, J=6.4 Hz, 2H), 2.20-2.10 (m, 2H).

Reference： [1]Linclau, Bruno; Peron, Florent; Bogdan, Elena; Wells, Neil; Wang, Zhong; Compain, Guillaume; Fontenelle, Clement Q.; Galland, Nicolas; Le Questel, Jean-Yves; Graton, Jérôme [Chemistry - A European Journal, 2015, vol. 21, # 49, p. 17808 - 17816]
[2]Liang, Jun; Zbieg, Jason R.; Blake, Robert A.; Chang, Jae H.; Daly, Stephen; Dipasquale, Antonio G.; Friedman, Lori S.; Gelzleichter, Thomas; Gill, Matthew; Giltnane, Jennifer M.; Goodacre, Simon; Guan, Jane; Hartman, Steven J.; Ingalla, Ellen Rei; Kategaya, Lorn; Kiefer, James R.; Kleinheinz, Tracy; Labadie, Sharada S.; Lai, Tommy; Li, Jun; Liao, Jiangpeng; Liu, Zhiguo; Mody, Vidhi; McLean, Neville; Metcalfe, Ciara; Nannini, Michelle A.; Oeh, Jason; O'Rourke, Martin G.; Ortwine, Daniel F.; Ran, Yingqing; Ray, Nicholas C.; Roussel, Fabien; Sambrone, Amy; Sampath, Deepak; Schutt, Leah K.; Vinogradova, Maia; Wai, John; Wang, Tao; Wertz, Ingrid E.; White, Jonathan R.; Yeap, Siew Kuen; Young, Amy; Zhang, Birong; Zheng, Xiaoping; Zhou, Wei; Zhong, Yu; Wang, Xiaojing [Journal of Medicinal Chemistry, 2021, vol. 64, # 16, p. 11841 - 11856]
[3]Current Patent Assignee: ROCHE HOLDING AG - US2017/362228, 2017, A1 Location in patent: Paragraph 0367; 0368

71
triphenyl(((1S,3R)-3-(((tetrahydro-2H-pyran-2-yl)oxy)methyl)cyclopentyl)methyl) phosphonium iodide [ No CAS ]
[ 19790-60-4 ]
2-(((1S,3R)-3-((E)-4-(benzyloxy)but-1-en-1-yl)cyclopentyl)methoxy)tetrahydro-2H-pyran [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
43%	Stage #1: triphenyl(((1S,3R)-3-(((tetrahydro-2H-pyran-2-yl)oxy)methyl)cyclopentyl)methyl) phosphonium iodide With n-butyllithium In tetrahydrofuran at 0℃; for 0.25h; Stage #2: 3-Benzyloxypropanal In tetrahydrofuran at 0 - 20℃; for 0.5h;
43%	With n-butyllithium In tetrahydrofuran at 0℃; for 0.5h;	2-(((1 S,3R)-3-( E)-4-(henzyioxv)hut- 1-en-I -yl)cyciopentvi)rnethoxy)tetrahydro-2F1- pyran (39) Compound 39 was synthesized by reaction of 22 (4.41 g. 752 mmoi) and 38 (1.45 g,9.02 rnmol) accordinu to the general procedure for Wittig olefination (see section 2.1). Olefin 39(1.10 g, 43%) was obtained as a colorless oil after purification by colunm chromatography onsilica gel using hexane/EtOAc (98:2 to 95:5) as eluent. Rf: 0.33 hexane/EtOAc 95:5); ‘H NMR(500 MHz, CDCI3-d,) d 7.32-7.24 (m. 5]). 549-5.30 (m, 2H), 4.57 (dd, J= 2.9, 4.2 Hz 1H),4.50 (s, 2H), 3.87-3.83 (rn, IH), 3.63-3.59 (m, 1H), 3.49-3.44 (rn, 3H), 3.29-3.24 (rn, IH), 2.79-2.71 (m, 0.8H). 2.44-2.22 (rn, 3.3H); 1.98-1.90 (m, 11-1), 1.84-1.66 (mn, 4H), 1.59-1.40 (m, SF1),1.34-1.24 (in, 1H), 1.00-0.89 (m, 1H); ‘C NMR (126 M1-Iz. CDCI3-d1) d 138.7, 138.6, 137.1,136.9, 128.4, 127.7, 127.6, 1247, 1244, 98.9, 72.9, 72.9, 724, 72.3, 72.2, 70.4, 703, 62.3, 62.2,43.7, 43.6, 41.7, 39.7, 39.4, 38.6, 38.5, 38.2, 38.0, 37.7, 37.5. 33.1, 32.8, 32.8, 32.3, 30.8, 29.0,28.9, 28.7, 28.4, 25.6, 19.7, 19.6.

Reference： [1]Koyanagi, Takaoki; Leriche, Geoffray; Onofrei, David; Holland, Gregory P.; Mayer, Michael; Yang, Jerry [Angewandte Chemie - International Edition, 2016, vol. 55, # 5, p. 1890 - 1893][Angew. Chem., 2015, p. 1922 - 1925,4]
[2]Current Patent Assignee: UNIVERSITY OF CALIFORNIA - WO2017/40702, 2017, A1 Location in patent: Paragraph 0450; 0465; 0466

72
[ 2449-05-0 ]
[ 19790-60-4 ]
[ 870621-16-2 ]
dibenzyl 1-((2S,3S,4R)-4-(benzoyloxy)-1-(benzyloxy)-3-hydroxyhex-5-en-2-yl)hydrazine-1,2-dicarboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	Stage #1: dibenzyl azodicarboxylate; 3-Benzyloxypropanal With D-Prolin In acetonitrile at 0℃; for 3h; Stage #2: (E)-3-benzoyloxyallyl bromide With ammonium chloride; zinc In water; acetonitrile at -20℃; for 2h; stereoselective reaction;	11 General experimental procedure for sequential a-amination/benzoyloxyallylation of Aldehydes General procedure: To a cooled solution of azadicarboxylate (5.0 mmol) and L-proline (10 mol%) in dry CH3CN (20 mL) at 0°C was added aldehydes (Formula Il(a-j)), 5 mmol) and the mixture was stirred for 3 h at 0°C. This was followed by the addition of zinc powder (7.5 mmol), 3-benzoyloxyallyl bromide (7.5 mmol) and saturated aq. NH4CI (20 ml) at -20°C for 2 h. The progress of the reaction can be monitored by TLC. After completion of the reaction, it was concentrated in vacuum to remove acetonitrile and the concentrate was extracted with ethyl acetate (3x40 mL). The combined organic layers were washed with brine, dried over anhyd. Na2S04, and concentrated under reduced pressure to give the crude products, which were then purified by flash column chromatography (100-200 mesh) using petroleum ether and ethyl acetate (4: 1) as eluents to afford the pure products of formula I(a-j).

Reference： [1]Current Patent Assignee: COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH (IN) - WO2016/13033, 2016, A1 Location in patent: Page/Page column 12; 18

73
[ 19790-60-4 ]
[ 191980-54-8 ]
3-(benzyloxy)-1-(1-trityl-1H-pyrazol-4-yl)propan-1-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		A solution of 4-iodo-l-trityl- lH-pyrazole (4.60 g, 10.5 mmol) in THF (50.0 mL) was purged with nitrogen 3 times. This was followed by dropwise addition of isopropylmagnesium bromide (2.9 M in THF, 4.18 mL, 12.1 mmol) at 0 C. The reaction mixture was stirred under a nitrogen atmosphere at 0 C for 1 h. To the reaction mixture was added a solution of 3-(benzyloxy)propanal (2.08 g, 12.7 mmol) in THF (3.0 mL) at 0 C. The resulting mixture was stirred at RT for 30 minutes. The reaction mixture was quenched with saturated NH4CI solution (2.0 mL), diluted with brine (30 mL) and extracted with ethyl acetate (3x10 mL). The combined organic extracts were dried over anhydrous Na2SC>4 and filtered. The filtrate was concentrated under vacuum. The residue was purified by silica gel chromatography (0 - 40% ethyl acetate in petroleum ether) to afford the title compound. MS = 497.1 (M+l).

Reference： [1]Patent: WO2016/154081,2016,A1 .Location in patent: Page/Page column 48

74
[ 1011267-44-9 ]
[ 19790-60-4 ]
[ 64-19-7 ]
(1R,2S,3S,4S,5S)-N-(3-(benzyloxy)propyl)-5-(1,2-dihydroxyethyl)-3,4-dihydroxybicyclo[3.1.0]hexan-2-ammonium acetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
69%	Stage #1: (1S,2S,3S,4S,5R)-4-amino-1-[(1S)-1,2-dihydroxyethyl]bicyclo[3.1.0]hexane-2,3-diol; 3-Benzyloxypropanal In methanol at 20℃; for 1h; Stage #2: With borane pyridine In methanol; aq. phosphate buffer at 0 - 20℃; Stage #3: acetic acid In methanol; aq. phosphate buffer	(1R,2S,3S,4S,5S)-N-(3-(Benzyloxy)propyl)-5-(1,2-dihydroxyethyl)-3,4-dihy-droxybicyclo[3.1.0]hexan-2-ammonium acetate (15) A solution of 2 (9.0 mg, 0.047 mmol) and 14 (7.8 mg, 0.047 mmol) in fresh CH3OH (2 mL) was stirred at rt for 1 h. To this mixture was added phosphate buffer (0.1 M, pH 6.8, 0.2 mL) and the solution was cooled to 0 °C before BH3*pyridine (20 mL, 0.16 mmol) wasadded. The reaction mixture was then warmed to rt and stirred overnight before being acidified with HOAc to pH 5 and concentrated. The resulting residue was purified by chromatography on Iatrobeads (CH2Cl2-CH3OH from 10:1 to 1:10) to give 15 (13.4 mg, 69%) as a white foam. Rf 0.48 (CH3OH-NH4OH 20:1); [α]25D +15.4 (c 0.47, CH3OH); 1H-NMR (500 MHz, CD3OD, δH) 7.35-7.24 (m,5H, Ar), 4.54 (d, 1H, J = 11.9 Hz, CH2Ph), 4.53 (d, 1H, J = 11.9 Hz, CH2Ph), 4.26 (d, 1H, J = 6.8 Hz, H-4),3.94 (dd, 1H, J = 6.4, 6.2 Hz, H-7), 3.83 (dd, 1H, J = 6.4, 6.8 Hz, H-3), 3.67-3.60 (m, 3H, H-8, CH2OBn),3.50 (dd, 1H, J = 6.4, 11.1 Hz, H-8), 3.46 (d, 1H, J = 6.4 Hz, H-2), 3.33-3.29 (m, 1H, 1 NHCH2), 3.10(ddd, 1H, J = 7.2, 7.2, 12.3 Hz, NHCH2), 2.11-1.97 (m, 4H, CH2CH2), 1.73 (dd, 1H, J = 4.0, 8.8 Hz, H-1),0.88 (dd, 1H, J = 5.7, 8.8 Hz, H-6), 0.75 (dd, 1H, J = 4.0, 5.7 Hz, H-6); 13C-NMR (125 MHz, CD3OD, δC)139.3 (Ar), 129.5 (2 C, Ar 2), 129.1 (2 C, Ar 2), 128.8 (Ar), 79.6 (C-4), 76.5 (C-3), 74.3 (CH2Ph), 71.9(C-7), 69.5 (CH2OBn), 66.0 (C-8), 60.9 (C-2), 46.5 (NHCH2), 35.9 (C-5), 27.6 (2 C, CH2CH2), 20.2 (C-1),8.6 (C-6). HRMS (ESI) m/z Calcd for (M - CH3COO-) C18H28NO5: 338.1962. Found: 338.1961.

Reference： [1]Lowary, Todd L.; Li, Jing [Molecules, 2016, vol. 21, # 8]

75
[ 19790-60-4 ]
[ 81290-20-2 ]
(4-(benzyloxy)-1,1,1-trifluorobutan-2-yloxy)trimethylsilane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%	With cesium fluoride In tetrahydrofuran at 20℃; for 2h;	175.2 Step 2: (4-(benzyloxy)-1, 1, 1-trifluorobutan-2-yloxy)trimethylsilane Step 2: (4-(benzyloxy)-1, 1, 1-trifluorobutan-2-yloxy)trimethylsilane To a solution of 3-(benzyloxy)propanal (4.0 g, 24.4 mmol) in THF (50 mL) was added trimethyl(trifluoromethyl)silane (10.4 g, 73.2 mmol) at rt, followed by the addition of CsF (0.37 g, 2.44 mmol). The resultant solution was stirred at rt for 2 hrs. Then quenched by water (100 ml) and extracted with EA (100 ml2), the organic phase was washed with water (100 mL2), and brine (100 mL), dried (Na2SO4), filtered and concentrated. The crude was purified by ISCO biotage to obtain (4-(benzyloxy)-1,1,1-trifluorobutan-2-yloxy)trimethylsilane as a colorless liquid. (4.5 g, 60%) 1H NMR (500 MHz, CDCl3) δ 7.38-7.29 (m, 5H), 4.51 (t, J=12 Hz, 2H), 4.23-4.19 (m, 1H), 3.59-3.57 (m, 2H), 2.04-2.01 (m, 1H), 1.78-1.73 (m, 1H), 0.13 (s, 9H).
4.5 g	With cesium fluoride In tetrahydrofuran at 20℃;	175.2 Step 2: (4-(benzyloxy)- 1, 1, 1-trifluorobutan-2-yloxy)trimethylsilane: To a solution of 3-(benzyloxy)propanal (4.0 g, 24.4 mmol) in THF (50 mL) wasadded trimethyl(trifluoromethyl)silane (10.4 g, 73.2 mmol) at rt, followed by the addition of CsF(0.37 g, 2.44 mmol). The resultant solution was stirred at rt for 2 hrs. Then quenched by water(100 ml) and extracted with EA (100 ml x 2), the organic phase was washed with water (100 mLx 2), and brine (100 mL), dried (Na2SO4), filtered and concentrated. The crude was purified byISCO biotage to obtain (4-(benzyloxy)-1, 1, 1-trifluorobutan-2-yloxy)trimethylsilane as acolorless liquid. (4.5 g, 60%)1H NMR (500 IVIFIz, CDC13) 7.38-7.29 (m, 5H), 4.51 (t, J= 12 Hz, 2 H), 4.23-4.19 (m, 1H), 3.59-3.57 (m, 2H), 2.04-2.01 (m, 1H), 1.78-1.73 (m, 1H), 0.13 (s, 9H).

Reference： [1]Current Patent Assignee: NAVITOR PHARM; NAVITOR PHARMACEUTICALS - US2017/114080, 2017, A1 Location in patent: Paragraph 0474; 0475
[2]Current Patent Assignee: NAVITOR PHARM; NAVITOR PHARMACEUTICALS - WO2018/200625, 2018, A1 Location in patent: Paragraph 00353; 00356; 00357

76
[ 5153-67-3 ]
[ 19790-60-4 ]
3-benzyloxymethyl-4-phenyl-5-nitro-1-formylcyclohexene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	With α,α-diphenyl-2-pyrrolidinemethanol trimethylsilyl ether In hexane at 0℃; for 24h;	1 3-benzyloxymethyl-5-nitro-4-phenyl-1-cyclohexene In the reaction flask was added 100mL 3-benzyloxy propanal (82.1mg, 0.5mmol), (E) - (2- nitro-vinyl) benzene (29.8mg, 0.2mmol), Catalyst C1 (13mg, 0.04mmol) and 10mL hexane, 0 placed stirred for 24 h, TLC the reaction was complete. The reaction mixture was concentrated by column chromatography (eluent: petroleum ether / ethyl acetate = 10/1 to 5/1) to give the desired product 3-benzyloxy-4- oxo-5-nitro-1-aromatic acyl cyclohexene 53mg, 75% yield

Reference： [1]Current Patent Assignee: QUZHOU UNIVERSITY - CN106905162, 2017, A Location in patent: Paragraph 0020-0021

77
[ 5153-67-3 ]
[ 19790-60-4 ]
[ 1186430-84-1 ]

Yield	Reaction Conditions	Operation in experiment
76%	With (2S)-2-{diphenyl[(trimethylsilyl)oxy]methyl}pyrrolidine In hexane at 0℃; for 24h;	2 (3S,4S,5S)-3-benzyloxymethyl-4-phenyl-5-nitro-1-formyl cyclohexene With the embodiment 1 similar method: in 100 ml reaction flask add 3 - benzyloxy propionaldehyde (82.1 mg, 0 . 5mmol), (E)- (2 - nitroethylene) benzene (29.8 mg, 0 . 2mmol), catalyst C2 (13 mg, 0 . 04mmol) and 10 ml hexane, is 0 °C stirring 24 hours, TLC detection reaction is complete. After concentrating the reaction column chromatography (eluent: petroleum ether/ethyl acetate=10/1 to 5/1) to obtain the target product (3S, 4S, 5S) -3 - benzyloxymethyl -4 - aromatic-based -5 - nitro -1 - formyl cyclohexene 53.5 mg, yield 76%

Reference： [1]Current Patent Assignee: QUZHOU UNIVERSITY - CN106905162, 2017, A Location in patent: Paragraph 0022-0023

78
[ 5153-67-3 ]
[ 19790-60-4 ]
(3R,4R,5R)-3-benzyloxymethyl-4-phenyl-5-nitro-1-formylcyclohexene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%	With (R)-2-(diphenyl(trimethylsilyloxy)methyl)pyrrolidine In hexane at 0℃; for 24h;	3 (3R, 4R, 5R) -3- benzyloxymethyl-nitro-1-phenyl-5-methyl-4-formyl-cyclohexene And a method similar to Example 1: In a reaction flask was added 100mL 3-benzyloxy propanal (82.1mg, 0.5mmol), (E) - (2- nitro-vinyl) benzene (29.8mg, 0.2mmol), the catalyst C3 (13mg, 0.04mmol) and 10mL of n-hexane, 0 placed stirred for 24 h, TLC the reaction was complete. The reaction mixture was concentrated by column chromatography (eluent: petroleum ether / ethyl acetate = 10 / 1to 5/1) to give the desired product (3R, 4R, 5R) -3- benzyloxycarbonylamino-5-methyl-4- aromatic - nitro-1-formyl-cyclohexene 53.4mg, yield 76%,> 99% ee.

Reference： [1]Current Patent Assignee: QUZHOU UNIVERSITY - CN106905162, 2017, A Location in patent: Paragraph 0024-0025

79
[ 109-06-8 ]
[ 19790-60-4 ]
4-(benzyloxy)-1-(pyridin-2-yl)butan-2-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
1.16 g	Stage #1: α-picoline With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.666667h; Stage #2: 3-Benzyloxypropanal In tetrahydrofuran; hexane at -30℃; for 1.16667h;	2-9-1 4-(benzyloxy)-1-(pyridin-2-yl)butan-2-amine To a solution of 2-methylpyridine (0.93 g) in tetrahydrofuran (5 mL) was added a solution of n-butyllithium in n-hexane (2.6 mol / L, 4.0 mL) at -78°C, and the mixture was stirred at the same temperature for 10 minutes and was stirred under ice-cooling for 0.5 hours. The reaction mixture was allowed to cool at -30°C. To the mixture was added dropwise a solution of 3-(benzyloxy)propanal (1.0 g) in tetrahydrofuran (2 mL), and the mixture was stirred at the same temperature for 10 minutes and was stirred under ice-cooling for 1 hour. To the reaction mixture was added water, and the crude product was extracted with ethyl acetate. The organic layer was washed with brine, and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane) to afford 4-(benzyloxy)-1-(pyridin-2-yl)butan-2-ol (1.16 g).
1.16 g	Stage #1: α-picoline With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Cooling with ice; Stage #2: 3-Benzyloxypropanal In tetrahydrofuran; hexane at -30℃; for 1.25h; Cooling with ice;	2-9-1 4- (Benzyloxy) -1- (pyridin-2-yl) butan-2-amine An n-butyllithium n-hexane solution (2.6 mol / L, 4.0 mL) was added at -78 ° C. to a tetrahydrofuran (5 mL) solution of 2-methylpyridine (0.93 g) And the mixture was stirred under ice-cooling for 0.5 hour.After cooling the reaction mixture to -30 ° C,3- (Benzyloxy) propanal (1.0 g)In tetrahydrofuran (2 mL) was added dropwise, and the mixture was stirred at the same temperature for 10 minutes and under ice-cooling for 1 hour. Water was added to the reaction mixture, and the crude product was extracted with ethyl acetate. The organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane)To give 4- (benzyloxy) -1- (pyridin-2-yl) butan-2-ol (1.16 g).Phthalimide (0.258 g), triphenylphosphine (0.459 g) and azodicarboxylic acid diethyl ester toluene solution (2.2 mol / L, 800 μL) were added to a tetrahydrofuran (2 mL) solution of the product (0.30 g) For 1 hour. The reaction mixture was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane)N- [4- (benzyloxy) -1- (pyridin-2-yl) butan-2-yl] phthalimide (0.45 g).Hydrazine monohydrate (0.58 g) was added to a methanol (3 mL) solution of the product (0.45 g), and the mixture was stirred under heating reflux for 4 hours. The reaction mixture was cooled to room temperature, then water was added and the crude product was extracted with dichloromethane. The organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by aminopropyl silica gel column chromatography (eluent: ethyl acetate / n-hexane) to give the title compound (0.10 g). Structural formula, spectral data and purification conditions are shown in Table 26.

Reference： [1]Current Patent Assignee: KISSEI PHARMACEUTICAL COMPANY LIMITED - EP3315492, 2018, A1 Location in patent: Paragraph 0198
[2]Current Patent Assignee: KISSEI PHARMACEUTICAL COMPANY LIMITED - JP2018/108988, 2018, A Location in patent: Paragraph 0215

80
[ 116-54-1 ]
[ 19790-60-4 ]
[ 17356-08-0 ]
[ 865776-75-6 ]

Yield	Reaction Conditions	Operation in experiment
71%	Stage #1: dichloroacetic acid methyl ester; 3-Benzyloxypropanal With sodium methylate In methanol; diethyl ether at 0℃; for 1.75h; Inert atmosphere; Stage #2: thiourea In methanol for 4h; Inert atmosphere; Reflux;
71%	Stage #1: dichloroacetic acid methyl ester; 3-Benzyloxypropanal With sodium methylate In methanol; diethyl ether at 0℃; for 1.75h; Inert atmosphere; Stage #2: thiourea In methanol for 4h; Reflux; Inert atmosphere;	7.II Methyl 2-amino-5-[2-(benzyloxy)ethyl]thiazole-4-carboxylate (90b): To an ice-cooled stirred solution of methyl 2,2-dichloroacetate (300 mT, 2.86 mmol, 1.1 equiv) and aldehyde 90a (500 mg, 3.04 mmol, 1.15 equiv) in Et20 (2.5 mL) was added a solution ofNaOMe [141 mg, 2.64 mmol, 1.0 equiv; in MeOH (2.5 mL)] dropwise over the period of 45 min and stirred for an additional 1 h at 0 °C. Then, the reaction mixture was extracted with Et20 (10 mL). The organic phase was washed with brine (10 mL), dried over Na2S04, and concentrated under reduced pressure. The obtained residue was disolve in MeOH (3 mL) and thiourea (170 mg, 2.24 mmol, 0.85 equiv) was added and heated to reflux for 4 h. The reaction mixture was then concentrated under reduced pressure, neutralize by the addition of NH4OH solution and extracted with CH2C12 (10 mL). The solution was washed with brine (10 mL), dried over Na2S04, and concentrated under reduced pressure. The obtained residue was purified by flash column chromatography (silica gel, 50 100% EtOAc in hexanes) to furnish compound 90b (632 mg, 2.16 mmol, 71% overall yield) as a colorless oil. 90b: Rf= 0.22 (silica gel, 70% EtOAc in hexanes); ' H NMR: (CDCL, 600 MHz) d 7.26-7.20 (m, 5 H), 5.38 (s, 2H), 4.45 (s, 2H), 3.76 (s, 3 H), 3.61 (t, = 6.1Hz, 2H), 3.34 (t, J= 6.1Hz, 2 H) ppm; 13C NMR: (CDC13, 150 MHz) d 164.6, 162.7, 137.9, 137.2, 136.3, 128.3, 127.5, 127.5, 72.9, 69.7, 51.8, 27.7 ppm.

Reference： [1]Nicolaou; Erande, Rohan D.; Yin, Jun; Vourloumis, Dionisios; Aujay, Monette; Sandoval, Joseph; Munneke, Stefan; Gavrilyuk, Julia [Journal of the American Chemical Society, 2018, vol. 140, # 10, p. 3690 - 3711]
[2]Current Patent Assignee: WILLIAM MARSH RICE UNIVERSITY - WO2019/108685, 2019, A1 Location in patent: Page/Page column 195

81
[ 19790-60-4 ]
C₉H₁₉NOS [ No CAS ]
(S)-N-((3R,4S,5S)-1-(benzyloxy)-3-hydroxy-5-methyl-4-heptane)-2-methylpropane-2-sulfinamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87%	With aluminum (III) chloride; strontium monoiodide; methyl iodide In tetrahydrofuran; <i>tert</i>-butyl alcohol at -78℃; for 8h;	2 Synthesis of (S)-N-((3R,4S,5S)-1-(benzyloxy)-3-hydroxy-5-methyl-4-heptane)-2-methylpropane-2-sulfinamide (4) Preparation of cerium diiodide solution (0.2 M in THF): 290 mL of tetrahydrofuran was added to freshly ground tantalum powder (9.6 g, 63.8 mmol).Diiodomethane (4.7 mL, 58.0 mmol) was added dropwise and stirred at room temperature for two hours.Compound 2 (2.4 g, 12.8 mmol), compound 3 (2.1 g, 12.8 mmol), tert-butanol (4.9 mL, 51.2 mmol) were dissolved in 250 mL of tetrahydrofuran and cooled to -78 degrees Celsius.Aluminum trichloride (69 μL, 1.28 mmol) was added, and a freshly prepared cesium diiodide solution (250 mL, 0.2 M in THF) was added. After stirring for 8 hours, the sodium thiosulfate pentahydrate solution was quenched.Extracted with ethyl acetate, dried, filtered, concentrated, and purified on a silica gel column to give a yellow oily liquid 4 (4.0 g, 87%).

Reference： [1]Current Patent Assignee: FUDAN UNIVERSITY - CN107954904, 2018, A Location in patent: Paragraph 0021; 0022; 0023; 0039; 0040

82
[ 19790-60-4 ]
[ 77385-90-1 ]
rac-(2SR,3RS)-5-benzyloxy-2-dibenzylamino-3-hydroxy-pentanoic acid ethyl ester [ No CAS ]
rac-(2RS,3RS)-5-benzyloxy-2-dibenzylamino-3-hydroxy-pentanoic acid ethyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
20%; 17%		a) racemic (2S,3R and 2R,3S)-5-Benzyloxy-2-dibenzylamino-3-hydroxy-pentanoic acid ethyl ester and racemic (2R,3R and 2S,3S)-5-Benzyloxy-2-dibenzylamino-3-hydroxy-pentanoic acid ethyl ester A solution of 42 g (148 mmol) dibenzylamino-acetic acid ethyl ester in 1 l tetrahydrofuran was stirred at -70 C. with 87 ml (77.6 mmol) lithium diisopropylamide (2M in tetrahydrofurane) for 60 minutes. 28.7 g (175 mmol) 3-(Benzyloxy)propanal were added and stirring was continued overnight. The mixture was allowed to warm to room temperature and 200 ml saturated aqueous ammonium chloride solution was added. Extraction with diethylether and chromatography on silicagel with ethylacetate/heptane 0:100 to 100:0 yielded as first eluding fraction 13.0 g (20%) racemic (2S,3R and 2R,3S)-5-benzyloxy-2-dibenzylamino-3-hydroxy-pentanoic acid ethyl ester, MS m/e (%): 448.1 (M+H+, 100) and as second diluting fraction 11.0 g (17%) racemic (2R,3R and 2S,3S)-5-benzyloxy-2-dibenzylamino-3-hydroxy-pentanoic acid ethyl ester, MS m/e (%): 448.1 (M+H+, 100).

Reference： [1]Patent: US2006/122168,2006,A1 .Location in patent: Page/Page column 52

83
2-[2-hydroxy-1-(hydroxymethyl)ethyl]isoindoline-1,3-dione [ No CAS ]
[ 19790-60-4 ]
2-(2-(2-(benzyloxy)ethyl)-trans-1,3-dioxan-5-yl)isoindoline-1,3-dione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
66%	With toluene-4-sulfonic acid In toluene at 110℃; Molecular sieve; Inert atmosphere;	2-(2-(2-(benzyloxy)ethyl)4rans-1 ,3-dioxan--5-yI)isoindoline--i,3-dione (9) A mixture of compound 6 (110 mg, 0.5 rnmol), compound 8 (83.7 rng, 0.5 mmol), ptoluenesuifonic acid (2 ing), 4A molecular sieve (20 mg) and toluene (4 mE) was stirred and heated at 110 °C under N2 atmosphere overnight. The mixture was filtered and washed withsaturated aqueous sodium bicarbonate. Phases were separated and the aqueous layer was extracted with dichioromethane. The organic layers were combined and concentrated. The crude product was purified by chromatography on silica gel with hexane/ethyl acetate (4:1) to give compound 9 as a white solid (122 mg). 1H NMR (CDCI3) : 1.96-2.02 (q, 2H); 3.61 (t, 2H); 3.99-4.04 (dd, 2H); 4.4 1-4.48 (t, 2H); 4.55 (s, 2H); 4.58-4.71 (m, 1H); 4.85 (t, 1H);7.28-7.36 (in, SF1); 7,74-7,77 (m, 2H) 7.83-7.87 (in, 2H).

Reference： [1]Current Patent Assignee: UNIVERSITY SYSTEM OF OHIO - WO2018/195098, 2018, A1 Location in patent: Page/Page column 38; 40

84
[ 67-56-1 ]
[ 19790-60-4 ]
[ 34591-97-4 ]

Reference： [1]Green Chemistry,2019,vol. 21,p. 669 - 674

85
[ 19790-60-4 ]
(R)-5-([2-methylbutyl]sulfonyl)-1-phenyl-1H-tetrazole [ No CAS ]
C₁₅H₂₂O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
71.1%	Stage #1: (R)-5-([2-methylbutyl]sulfonyl)-1-phenyl-1H-tetrazole With lithium hexamethyldisilazane In tetrahydrofuran at -78℃; for 1h; Inert atmosphere; Stage #2: 3-Benzyloxypropanal In tetrahydrofuran for 5h;	1 Preparation of Compound E: Compound B (5 g, 17.84 mmol) and 30 mL of anhydrous tetrahydrofuran were weighed.The mixture was argon-protected in a 250 mL two-necked flask, and LiHMDS (1 M solution 21.40 mL, 21.40 mmol) was slowly added dropwise at -78 ° C, and stirred for 1 h.15 mL of a solution of Compound D (3.51 g, 21.40 mmol) in tetrahydrofuran was added dropwise.Stir for 5 h, the reaction was complete by TLC; the reaction was quenched with saturated ammonium chloride.The aqueous phase was extracted three times with diethyl ether. The organic phases were combined and washed with saturated NaCI.Dry over anhydrous magnesium sulfate, spin dry solvent, petroleum ether to give 2.77 g of compound E.The yield is 71.1%

Reference： [1]Current Patent Assignee: NORTHWEST A&F UNIVERSITY - CN109265327, 2019, A Location in patent: Paragraph 0041; 0056; 0066

86
[ 7188-38-7 ]
[ 19790-60-4 ]
[ 37566-39-5 ]
6-[2-(benzyloxy)ethyl]-2-bromo-N-(tert-butyl)imidazo[2,1-b][1,3,4]thiadiazole-5-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
38%	Stage #1: 3-Benzyloxypropanal; 5-bromo-2-amino-1,3,4-thiadiazole In butan-1-ol at 20℃; for 0.166667h; Stage #2: tert-butylisonitrile With magnesium chloride In butan-1-ol at 0 - 70℃; for 5h;	86.1 STEP 1) 6-[2-(benzyloxy)ethyl]-2-bromo-N-(tert-butyl)imidazo[2,1-b][1,3,4]thiadiazole-5-amine 3-(benzyloxy)n-propanal (6.9 g, 42.07 mmol) was added to 5-bromo-1,3,4-thiadiazole-2-amine (4.7 g, 26.26 mmol) in n-butanol (60 mL).The mixture was stirred at room temperature for 10 minutes until the temperature decreased to 0 °C. Magnesium chloride (1.28 g, 13.47 mmol) and butyl isocyanide (2.28 g, 27.47 mmol) were added. After the temperature increased to 70 °C, the mixture was reacted for 5 hours and LC-MS detection indicated that the reaction was completed. The reaction mixture was evaporated and water (60 mL) was added to it, which was further extracted with ethyl acetate (60 mL x 2). The organic layer was combined, washed with saturated saline solution, dried with anhydrous sodium sulfate, evaporated, and purified through column purification (petroleum ether: ethyl acetate= 3:1), to obtain 4.1 g of an oily product, yield: 38%. MS (m/z): 409.1, 411.1 [M+1].

Reference： [1]Current Patent Assignee: GUANGZHOU HENOVCOM BIOSCIENCE - EP3805234, 2021, A1 Location in patent: Paragraph 0364

87
[ 590-18-1 ]
[ 19790-60-4 ]
[ 909803-71-0 ]

Yield	Reaction Conditions	Operation in experiment
74%	Stage #1: (Z)-2-Butene With n-butyllithium; potassium <i>tert</i>-butylate In tetrahydrofuran at -78 - -45℃; for 0.5h; Stage #2: 3-Benzyloxypropanal With boron trifluoride diethyl etherate; (+)-B-methoxydiisocamphenylborane In tetrahydrofuran at -78℃; for 8h;	[00224] cA-2-butene (9.03mL, 103. mmol, 2.00 equiv) was condensed in a 450 mL round bottom flask containing potassium /c/7-but oxide (45.5 mL, 77.4 mmol, 1.70 M in tetrahydrofuran, 1.50 equiv) at -78 °C. The resultant mixture was added freshly titrated n-butyl lithium (31.0 mL, 77.4 mmol, 2.5 M, 2.00 equiv) dropwise, and was warmed to -45 °C for 30 minutes. The yellow-orange solution was cooled to -78 °C, and a solution of /.-(+)-B-methoxydiisopinocampheylborane (24.5 g, 77.4 mmol, 1.50 equiv) in tetrahydrofuran (150 mL) was added dropwise. After stirring at -78 °C for 30 min, boron trifluoride diethyl etherate (9.55 mL, 77.4 mmol, 1.50) was added dropwise to the reaction mixture, followed by immediately addition of a solution of aldehyde S8 (8.47 g, 51.6 mmol, 1.00 equiv) in tetrahydrofuran (150 mL) at the -78 °C using syringe pump (20 mL/hr). After complete addition, the reaction was stirred for 8 h at -78 °C. The reaction was quenched by addition of anhydrous methanol (10.4 mL, 258. mmol, 5.00 equiv) and warmed up to 24 °C slowly. The resulting sticky mixture was concentrated under reduced pressure, and the gummy residue was redissolved in a 1:1 mixture (tetrahydrofuran/ water, 500 mL). Hydrogen peroxide (12.1 mL, 516. mmol, 35%, 10.00 equiv) was added to the solution at 0 °C portionwise, and the mixture was warmed to 24 °C slowly. The mixture was stirred continuously at 24 °C for 8 h, followed by heating at 65 °C for 3 h. The mixture was cooled to 24 °C and diluted with water (500 mL). The mixture was partitioned in a separaratory funnel with ethyl acetate (500 mL). The layers were separated, and the aqueous layer was extracted with ethyl acetate (2 x 200 mL). The combined organic layer was dried over anhydrous sodium sulfate. The dried solution was filtered a plug of cotton. The filtrate was concentrated under reduced pressure. The crude product was purified by column chromatography to give the secondary alcohol (8.30 g, 74%).

Reference： [1]Current Patent Assignee: HARVARD UNIVERSITY - WO2021/142115, 2021, A1 Location in patent: Paragraph 00224

88
[ 766-83-6 ]
[ 19790-60-4 ]
5-(benzyloxy)-1-(3-chlorophenyl)pent-1-yn-3-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
94%	Stage #1: 3-chlorophenylacetylene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: 3-Benzyloxypropanal In tetrahydrofuran; hexane at 20℃; for 1h; Inert atmosphere;

Reference： [1]Chen, Liang-An; Dai, Mengfu; Sun, Zhimin [Angewandte Chemie - International Edition, 2022, vol. 61, # 23][Angew. Chem., 2022, vol. 134, # 23]

Purity	Size	Price	VIP Price	USA Stock *0-1 Day	Global Stock *5-7 Days	Quantity
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CAS No. :	19790-60-4	MDL No. :	MFCD00506599
Formula :	C₁₀H₁₂O₂	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	ANSYAMHYCYOWAW-UHFFFAOYSA-N
M.W :	164.20	Pubchem ID :	10888261
Synonyms :

Num. heavy atoms :	12
Num. arom. heavy atoms :	6
Fraction Csp3 :	0.3
Num. rotatable bonds :	5
Num. H-bond acceptors :	2.0
Num. H-bond donors :	0.0
Molar Refractivity :	47.11
TPSA :	26.3 Å²

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	No
CYP1A2 inhibitor :	Yes
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-6.43 cm/s

Log Po/w (iLOGP) :	1.86
Log Po/w (XLOGP3) :	1.23
Log Po/w (WLOGP) :	1.64
Log Po/w (MLOGP) :	1.47
Log Po/w (SILICOS-IT) :	2.53
Consensus Log Po/w :	1.75

[ CAS No. 19790-60-4 ] {[proInfo.proName]}

Quality Control of [ 19790-60-4 ]

Related Doc. of [ 19790-60-4 ]

Product Details of [ 19790-60-4 ]

Calculated chemistry of [ 19790-60-4 ]

Physicochemical Properties

Pharmacokinetics

Lipophilicity

Druglikeness

Water Solubility

Medicinal Chemistry

Safety of [ 19790-60-4 ]

Application In Synthesis of [ 19790-60-4 ]

[ 19790-60-4 ] Synthesis Path-Upstream 1~1

[ 19790-60-4 ] Synthesis Path-Downstream 1~88

Related Functional Groups of
[ 19790-60-4 ]

Aryls

Aldehydes

Ethers

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry

Lipinski :	0.0
Ghose :	None
Veber :	0.0
Egan :	0.0
Muegge :	1.0
Bioavailability Score :	0.55

Log S (ESOL) :	-1.67
Solubility :	3.49 mg/ml ; 0.0212 mol/l
Class :	Very soluble
Log S (Ali) :	-1.38
Solubility :	6.85 mg/ml ; 0.0417 mol/l
Class :	Very soluble
Log S (SILICOS-IT) :	-3.29
Solubility :	0.084 mg/ml ; 0.000512 mol/l
Class :	Soluble

PAINS :	0.0 alert
Brenk :	1.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	1.43

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P261-P305+P351+P338	UN#:	N/A
Hazard Statements:	H315-H319-H335	Packing Group:	N/A
GHS Pictogram:

Precautionary Statements-General
Code	Phrase
P101	If medical advice is needed,have product container or label at hand.
P102	Keep out of reach of children.
P103	Read label before use
Prevention
Code	Phrase
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P211	Do not spray on an open flame or other ignition source.
P220	Keep/Store away from clothing/combustible materials.
P221	Take any precaution to avoid mixing with combustibles
P222	Do not allow contact with air.
P223	Keep away from any possible contact with water, because of violent reaction and possible flash fire.
P230	Keep wetted
P231	Handle under inert gas.
P232	Protect from moisture.
P233	Keep container tightly closed.
P234	Keep only in original container.
P235	Keep cool
P240	Ground/bond container and receiving equipment.
P241	Use explosion-proof electrical/ventilating/lighting/equipment.
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P262	Do not get in eyes, on skin, or on clothing.
P263	Avoid contact during pregnancy/while nursing.
P264	Wash hands thoroughly after handling.
P265	Wash skin thouroughly after handling.
P270	Do not eat, drink or smoke when using this product.
P271	Use only outdoors or in a well-ventilated area.
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P280	Wear protective gloves/protective clothing/eye protection/face protection.
P281	Use personal protective equipment as required.
P282	Wear cold insulating gloves/face shield/eye protection.
P283	Wear fire/flame resistant/retardant clothing.
P284	Wear respiratory protection.
P285	In case of inadequate ventilation wear respiratory protection.
P231 + P232	Handle under inert gas. Protect from moisture.
P235 + P410	Keep cool. Protect from sunlight.
Response
Code	Phrase
P301	IF SWALLOWED:
P304	IF INHALED:
P305	IF IN EYES:
P306	IF ON CLOTHING:
P307	IF exposed:
P308	IF exposed or concerned:
P309	IF exposed or if you feel unwell:
P310	Immediately call a POISON CENTER or doctor/physician.
P311	Call a POISON CENTER or doctor/physician.
P312	Call a POISON CENTER or doctor/physician if you feel unwell.
P313	Get medical advice/attention.
P314	Get medical advice/attention if you feel unwell.
P315	Get immediate medical advice/attention.
P320
P302 + P352	IF ON SKIN: wash with plenty of soap and water.
P321
P322
P330	Rinse mouth.
P331	Do NOT induce vomiting.
P332	IF SKIN irritation occurs:
P333	If skin irritation or rash occurs:
P334	Immerse in cool water/wrap n wet bandages.
P335	Brush off loose particles from skin.
P336	Thaw frosted parts with lukewarm water. Do not rub affected area.
P337	If eye irritation persists:
P338	Remove contact lenses, if present and easy to do. Continue rinsing.
P340	Remove victim to fresh air and keep at rest in a position comfortable for breathing.
P341	If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P342	If experiencing respiratory symptoms:
P350	Gently wash with plenty of soap and water.
P351	Rinse cautiously with water for several minutes.
P352	Wash with plenty of soap and water.
P353	Rinse skin with water/shower.
P360	Rinse immediately contaminated clothing and skin with plenty of water before removing clothes.
P361	Remove/Take off immediately all contaminated clothing.
P362	Take off contaminated clothing and wash before reuse.
P363	Wash contaminated clothing before reuse.
P370	In case of fire:
P371	In case of major fire and large quantities:
P372	Explosion risk in case of fire.
P373	DO NOT fight fire when fire reaches explosives.
P374	Fight fire with normal precautions from a reasonable distance.
P376	Stop leak if safe to do so. Oxidising gases (section 2.4) 1
P377	Leaking gas fire: Do not extinguish, unless leak can be stopped safely.
P378
P380	Evacuate area.
P381	Eliminate all ignition sources if safe to do so.
P390	Absorb spillage to prevent material damage.
P391	Collect spillage. Hazardous to the aquatic environment
P301 + P310	IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician.
P301 + P312	IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell.
P301 + P330 + P331	IF SWALLOWED: Rinse mouth. Do NOT induce vomiting.
P302 + P334	IF ON SKIN: Immerse in cool water/wrap in wet bandages.
P302 + P350	IF ON SKIN: Gently wash with plenty of soap and water.
P303 + P361 + P353	IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower.
P304 + P312	IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell.
P304 + P340	IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing.
P304 + P341	IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P305 + P351 + P338	IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing.
P306 + P360	IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes.
P307 + P311	IF exposed: call a POISON CENTER or doctor/physician.
P308 + P313	IF exposed or concerned: Get medical advice/attention.
P309 + P311	IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician.
P332 + P313	IF SKIN irritation occurs: Get medical advice/attention.
P333 + P313	IF SKIN irritation or rash occurs: Get medical advice/attention.
P335 + P334	Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages.
P337 + P313	IF eye irritation persists: Get medical advice/attention.
P342 + P311	IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician.
P370 + P376	In case of fire: Stop leak if safe to Do so.
P370 + P378	In case of fire:
P370 + P380	In case of fire: Evacuate area.
P370 + P380 + P375	In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion.
P371 + P380 + P375	In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion.
Storage
Code	Phrase
P401
P402	Store in a dry place.
P403	Store in a well-ventilated place.
P404	Store in a closed container.
P405	Store locked up.
P406	Store in corrosive resistant/ container with a resistant inner liner.
P407	Maintain air gap between stacks/pallets.
P410	Protect from sunlight.
P411
P412	Do not expose to temperatures exceeding 50 oC/ 122 oF.
P413
P420	Store away from other materials.
P422
P402 + P404	Store in a dry place. Store in a closed container.
P403 + P233	Store in a well-ventilated place. Keep container tightly closed.
P403 + P235	Store in a well-ventilated place. Keep cool.
P410 + P403	Protect from sunlight. Store in a well-ventilated place.
P410 + P412	Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF.
P411 + P235	Keep cool.
Disposal
Code	Phrase
P501	Dispose of contents/container to ...
P502	Refer to manufacturer/supplier for information on recovery/recycling