[ CAS No. 586-95-8 ] {[proInfo.proName]}

Name: 586-95-8|4-Pyridinemethanol|99% HPLC
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2D 3D

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Quality Control of [ 586-95-8 ]

COA NMR CNMR HPLC LC-MS

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SDS Specification

Alternatived Products of [ 586-95-8 ]

Product Details of [ 586-95-8 ]

CAS No. :	586-95-8	MDL No. :	MFCD00006442
Formula :	C₆H₇NO	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	PTMBWNZJOQBTBK-UHFFFAOYSA-N
M.W :	109.13	Pubchem ID :	11472
Synonyms :

Calculated chemistry of [ 586-95-8 ]

Physicochemical Properties

Num. heavy atoms :	8
Num. arom. heavy atoms :	6
Fraction Csp3 :	0.17
Num. rotatable bonds :	1
Num. H-bond acceptors :	2.0
Num. H-bond donors :	1.0
Molar Refractivity :	30.36
TPSA :	33.12 Å²

Pharmacokinetics

GI absorption :	High
BBB permeant :	No
P-gp substrate :	No
CYP1A2 inhibitor :	No
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-6.92 cm/s

Lipophilicity

Log Po/w (iLOGP) :	1.24
Log Po/w (XLOGP3) :	0.06
Log Po/w (WLOGP) :	0.42
Log Po/w (MLOGP) :	-0.14
Log Po/w (SILICOS-IT) :	1.25
Consensus Log Po/w :	0.57

Druglikeness

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

Water Solubility

Log S (ESOL) :	-1.04
Solubility :	9.88 mg/ml ; 0.0905 mol/l
Class :	Very soluble
Log S (Ali) :	-0.31
Solubility :	53.6 mg/ml ; 0.491 mol/l
Class :	Very soluble
Log S (SILICOS-IT) :	-1.79
Solubility :	1.77 mg/ml ; 0.0162 mol/l
Class :	Soluble

Medicinal Chemistry

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

Safety of [ 586-95-8 ]

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P261-P305+P351+P338	UN#:	N/A
Hazard Statements:	H302-H315-H319-H335	Packing Group:	N/A
GHS Pictogram:

Application In Synthesis of [ 586-95-8 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

Upstream synthesis route of [ 586-95-8 ]
Downstream synthetic route of [ 586-95-8 ]

[ 586-95-8 ] Synthesis Path-Upstream 1~13

1
[ 586-95-8 ]
[ 6457-49-4 ]

Reference： [1] Journal fuer Praktische Chemie (Leipzig), 1938, vol. <2> 151, p. 65,79
[2] Patent: US2003/55244, 2003, A1,

2
[ 586-95-8 ]
[ 63608-14-0 ]
[ 6457-49-4 ]

Reference： [1] Patent: US4243807, 1981, A,

3
[ 1003-67-4 ]
[ 108-24-7 ]
[ 1121-19-3 ]
[ 586-95-8 ]

Reference： [1] Journal of Medicinal Chemistry, 1987, vol. 30, # 11, p. 2031 - 2046

4
[ 586-95-8 ]
[ 67-56-1 ]
[ 2459-09-8 ]

Reference： [1] Synthesis, 2003, # 7, p. 1055 - 1064
[2] Green Chemistry, 2014, vol. 16, # 4, p. 2164 - 2173

5
[ 586-95-8 ]
[ 69583-00-2 ]

Reference： [1] ChemMedChem, 2015, vol. 10, # 11, p. 1875 - 1883

6
[ 2459-09-8 ]
[ 586-95-8 ]
[ 26156-51-4 ]
[ 58481-17-7 ]
[ 82828-86-2 ]

Reference： [1] Bulletin of the Chemical Society of Japan, 1984, vol. 57, # 7, p. 1882 - 1886

7
[ 2459-09-8 ]
[ 586-95-8 ]
[ 26156-51-4 ]
[ 58481-17-7 ]
[ 82828-86-2 ]

Reference： [1] Bulletin of the Chemical Society of Japan, 1984, vol. 57, # 7, p. 1882 - 1886

8
[ 6342-46-7 ]
[ 586-95-8 ]
[ 104-86-9 ]

Reference： [1] Bulletin of the Chemical Society of Japan, 1988, vol. 61, p. 1397 - 1398

9
[ 586-95-8 ]
[ 75-91-2 ]
[ 872-85-5 ]
[ 81660-73-3 ]

Reference： [1] Journal of Organic Chemistry, 1996, vol. 61, # 4, p. 1467 - 1472

10
[ 586-95-8 ]
[ 1822-51-1 ]

Yield	Reaction Conditions	Operation in experiment
100%	With thionyl chloride In acetonitrile at 50℃; for 1 h;	4-Chloromethylpyridine Hydrochloride (21); EMI35.0[0161] 4-Hydroxymethylpyridine (20) (54.4 g, 0.50 mol) was dissolved in acetonitrile 202 ml. The solution was added dropwise to a mixture of thionyl chloride (65.3 g, 0.55 mol) and acetonitrile (109 ml) under 50[deg.] C. The mixture was stirred at the same temperature for 1 hour, then cooled to room temperature to yield a slurry (quantitative) of the objective (21). [0162] <1>H-NMR (DMSO-TMS) [delta] ppm: 5.09 (s, 2H), 8.09 (d, J=6.6 Hz, 2H), 8.94 (d, J=6.6 Hz, 2H).

Reference： [1] Patent: US2003/195363, 2003, A1, . Location in patent: Page/Page column 13
[2] Patent: US6057448, 2000, A,
[3] ChemMedChem, 2015, vol. 10, # 11, p. 1875 - 1883

11
[ 586-95-8 ]
[ 73870-24-3 ]

Yield	Reaction Conditions	Operation in experiment
58.1%	With phosphorus pentabromide In chloroform	67a 4-bromomethyl pyridine hydrobromide To a solution of 4-pyridylcarbinol (3 g, 27.5 mmol) in 30 mL of CHCl₃ was added phosphorus pentabromide (5.93 g, 13.7 mmol). The solution was refluxed for 1 hour. The solvent was removed in vacuo and recrystallized in ethanol to afford the title compound as a white solid (4.05 g, 58.1percent). ES (+) MS m/e=173 (M+H).

Reference： [1] Patent: US6403792, 2002, B1,
[2] Angewandte Chemie - International Edition, 2017, vol. 56, # 38, p. 11640 - 11644[3] Angew. Chem., 2017, vol. 129, # 38, p. 11799 - 11803,5
[4] Patent: US2010/152160, 2010, A1, . Location in patent: Page/Page column 81
[5] Chemical Communications, 2011, vol. 47, # 5, p. 1482 - 1484

12
[ 586-95-8 ]
[ 65737-59-9 ]

Reference： [1] Chemical Communications, 2011, vol. 47, # 5, p. 1482 - 1484
[2] Journal of the American Chemical Society, 2018, vol. 140, # 9, p. 3322 - 3330

13
[ 586-95-8 ]
[ 152121-47-6 ]

Reference： [1] Bioorganic and Medicinal Chemistry, 1997, vol. 5, # 1, p. 49 - 64

[ 586-95-8 ] Synthesis Path-Downstream 1~66

1
[ 586-95-8 ]
[ 872-85-5 ]

Yield	Reaction Conditions	Operation in experiment
85%	With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; sodium hydrogencarbonate; In dichloromethane; water; at 20℃; for 6h;Green chemistry;	General procedure: A mixture of H2O (5 mL) and CH2Cl2 (5 mL) wasadded to the chlorinated polymeric beads (2 g). (The unchlorinated beads were obtained from HaloSource, Inc. The unchlorinated beads were chlorinated by soaking the beads in bleach solution, with pH adjusted to 7 by additionof AcOH, for an hour. Then, the chlorinated beads were filtered and dried in air.) After addition of TEMPO (10 mg,0.064 mmol) and benzyl alcohol (0.2 g, 1.8 mmol), NaHCO3(0.5 g) was added to the mixture. The mixture was stirred at r.t. for 3 h and filtered. The residue on the filter paper was washed with H2O (20 mL) and CH2Cl2 (10 mL), and the organic phase of the filtrate was separated, dried over MgSO4, and filtered. The solvent was removed under vacuum to obtain benzaldehyde.
85.5%	With dihydrogen peroxide; In water; at 80℃; for 5h;Green chemistry;	General procedure: The selective oxidation of benzyl alcohol using aqueous H2O2 without organic solvents and additives was chosen as the probe reaction to test the activities of as-prepared catalysts. Typically, benzyl alcohol (0.5mmol), H2O2 (30wt%, 0.6mmol), deionized water (1ml), catalyst (10mg) were added sequentially into a sealed glass tube with vigorous magnetic stirring at 80 for 3h. After the reaction, the solid catalyst was separated by centrifugation, and then washed with deionized water and ethanol thoroughly, followed by drying at 60 in vacuum oven overnight for reuse. The filtrate was extracted by ethyl acetate and then analyzed by GC (Agilent 6820, FID detector, 30m hp-5 capillary column) with external standard method, and the products were identified through comparison with known standards. Additionally, to ensure the reproducibility of all activity tests, each result had been repeated at least three times and found to be within acceptable error ranges (±2.0%).
74%	With C26H16N6O4Ru; dihydrogen peroxide; at 60℃; for 1h;	General procedure: The catalytic oxidation of alcohol was carried out in a magnetically stirredglass reaction tube fitted with a reflux condenser. A typical procedure was asfollows using benzyl alcohol as model substrate: benzyl alcohol (2 mmol) andRu(bbp)(pydic) (2 103 mmol, 0.1 mol % based substrate) were added into areaction tube. The reactor containing this mixture was heated to 60 C in an oilbath under vigorous stirring, and then 30% H2O2 (10 mmol) was slowlydropped in. The resulting system was stirred at 60 C for 60 min. At the end ofreaction, the resulting products and unreacted substrate were extracted bydichloromethane three times. The extracted liquid mixture was analyzed byGC and GC-MS. GC analyses were performed on a Shimadzu GC-2010 pluschromatography equipped with Rtx-5 capillary column(30 m 0.25 mm 0.25 lm). GC-MS analyses were recorded on a ShimadzuGCMS-QP2010 equipped with Rxi-5 ms capillary column(30 m 0.25 mm 0.25 lm).

53%	With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; In n-heptane; at 80℃; under 760.051 Torr; for 24h;	General procedure: A mixture of catalyst PS-PEG-TD2-Cu(OAc)2 (100 mg, 0.05mmol Cu), BnOH (1a, 27.0 mg, 0.25 mmol), and TEMPO (7.8 mg,0.05 mmol) in heptane (2.0 mL) was stirred at 80 C for 24 hunder air (1 atm). The mixture was then cooled and filtered, andthe resulting solid material was washed with Et2O (3 × 2 mL).The organic phases were combined, concentrated to a volume of2 mL, and the internal standard was added to determine the GCyield. The crude product was purified by column chromatography[silica gel, hexane-Et2O (99:1)]. In the formation of somebenzaldehydes, low isolated yields were observed because ofinstability of the benzaldehydes on silica gel
52%	With Nitrogen dioxide; In acetonitrile; at 120℃; under 760.051 Torr; for 5h;Sealed tube;	General procedure: To a dried 45 mL tube equipped with a magnetic stirring, 2 mL acetonitrile, 0.5 mmol substrate and 0.046 mmol NO2 were sequentially added (note: the air in the tube was not removed). Then the reaction tube was sealed and stirred magnetically at a constant-temperature to perform the reaction for 5 h. Once the reaction time was reached, GCanalysis of the mixture provided the GC yields of the products. Then the crude product from another parallel experiment was purified by silicagel chromatography to give the desired product.
26%	With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; [Cu2(1,2-benzenedicarboxylate)2(1,4-bis(1,2,4-triazol-1-ylmethyl)-2,3,5,6-tetrafluorobenzene)2]·3H2O}n; sodium carbonate; In acetonitrile; at 75℃; for 16h;	General procedure: In a typical experiment, 4-methoxybenzyl alcohol (12muL, 0.1mmol), Cu-FMOF (11.3mg, 10mmol %), TEMPO (7.8mg, 0.05mmol) and NaCO3 (10.6mg, 0.1mmol) in 1mL of air saturated acetonitrile were taken in a 15-mL three-necked round-bottom flask. The solution was magnetically stirred for 16h at 75C under air atmosphere. The progress of the reaction was monitored via gas chromatography (Shimadzu GC-2010AF) involving a Chromopak capillary column and flame ionization detector. The products were further confirmed by using gas chromatography-mass spectroscopy (GC-MS) (Shimadzu GCMS-2010). The concentrations of 4-methoxybenzyl alcohol and 4-methoxybenzylaldehyde were calibrated by external standard method with standard samples (see Fig. S1).
	With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione; In dimethyl sulfoxide; at 20℃;	In a typical experiment, the primary alcohol (0.5-0.6 mmol) and IBX (1.1 equiv) were stirred in DMSO at ca. 20 C. Once the oxidation of alcohol to aldehyde was complete, as judged from TLC analysis, o-phenylenediamine (1.1 equiv) was introduced into the reaction mixture and the reaction mixture was allowed to stir at room temperature until the aldehyde disappeared. At the end of the reaction, DMSO was removed under high vacuum, and the residue was treated with 1.0 M NaHCO3 solution until the pH was 8-9. The organic matter was extracted with ethyl acetate. Regular work-up followed by silica-gel column chromatography led to pure benzimidazoles, which were characterized spectroscopically.

Reference： [1]Journal of Chemical Research,2007,p. 252 - 256
[2]Chinese Journal of Chemistry,2020
[3]Bulletin of the Chemical Society of Japan,1991,vol. 64,p. 796 - 800
[4]Phosphorus, Sulfur and Silicon and the Related Elements,2007,vol. 182,p. 589 - 593
[5]Tetrahedron Letters,1999,vol. 40,p. 1635 - 1636
[6]Chemistry - An Asian Journal,2016,vol. 11,p. 3084 - 3089
[7]Synthesis,1988,p. 868 - 871
[8]European Journal of Organic Chemistry,2014,vol. 2014,p. 395 - 402
[9]Synlett,2013,vol. 24,p. 2451 - 2453
[10]Applied Catalysis A: General,2018,vol. 558,p. 26 - 33
[11]Synthetic Communications,2004,vol. 34,p. 2835 - 2842
[12]Journal of Organic Chemistry,2002,vol. 67,p. 7075 - 7079
[13]New Journal of Chemistry,2017,vol. 41,p. 2372 - 2377
[14]Inorganic Chemistry,2020,vol. 59,p. 254 - 263
[15]Journal of Chemical Research,2006,p. 188 - 191
[16]Tetrahedron Letters,2005,vol. 46,p. 8483 - 8486
[17]Tetrahedron Letters,2013,vol. 54,p. 3882 - 3885
[18]New Journal of Chemistry,2017,vol. 41,p. 13377 - 13381
[19]New Journal of Chemistry,2019,vol. 43,p. 19415 - 19421
[20]Synlett,2018,vol. 29,p. 1152 - 1156
[21]Catalysis Communications,2017,vol. 101,p. 98 - 101
[22]Catalysis Communications,2017,vol. 95,p. 6 - 11
[23]Chemische Berichte,1990,vol. 123,p. 1357 - 1364
[24]Justus Liebigs Annalen der Chemie,1958,vol. 613,p. 171,179
[25]Pharmaceutical Bulletin,1955,vol. 3,p. 232
[26]Justus Liebigs Annalen der Chemie,1958,vol. 613,p. 171,179
[27]Justus Liebigs Annalen der Chemie,1958,vol. 613,p. 171,179
[28]Recueil des Travaux Chimiques des Pays-Bas,1952,vol. 71,p. 970,974
[29]Pharmaceutical Bulletin,1954,vol. 2,p. 341
[30]Journal of Organic Chemistry USSR (English Translation),1985,vol. 21,p. 588 - 591
Zhurnal Organicheskoi Khimii,1985,vol. 21,p. 649 - 652
[31]Journal of Organic Chemistry,1996,vol. 61,p. 1467 - 1472
[32]European Journal of Organic Chemistry,2010,p. 3445 - 3448
[33]Tetrahedron Letters,2011,vol. 52,p. 3868 - 3871
[34]ChemMedChem,2014,vol. 9,p. 590 - 601
[35]Journal of the Chinese Chemical Society,2014,vol. 61,p. 517 - 520
[36]European Journal of Organic Chemistry,2014,vol. 2014,p. 395 - 402
[37]RSC Advances,2016,vol. 6,p. 106769 - 106777
[38]Patent: CN107311918,2017,A .Location in patent: Paragraph 0032; 0036; 0041; 0046
[39]Tetrahedron Letters,2018,vol. 59,p. 247 - 251
[40]New Journal of Chemistry,2018,vol. 42,p. 11381 - 11389
[41]Applied Organometallic Chemistry,2018,vol. 32
[42]Zeitschrift fur Anorganische und Allgemeine Chemie,2018,vol. 644,p. 692 - 699
[43]New Journal of Chemistry,2018,vol. 42,p. 16523 - 16532
[44]Inorganica Chimica Acta,2019,vol. 486,p. 476 - 482
[45]ChemBioChem,2019,vol. 20,p. 276 - 281
[46]Patent: CN106866508,2019,B .Location in patent: Paragraph 0015-0018
[47]Inorganic Chemistry Communications,2020,vol. 112
[48]Chemistry - An Asian Journal,2020,vol. 15,p. 926 - 932
[49]Electrochimica Acta,2020,vol. 354
[50]Molecular catalysis,2020,vol. 494
[51]Catalysis Communications,2020,vol. 145
[52],2020,vol. 10,p. 7699 - 7709

2
[ 586-95-8 ]
[ 10445-91-7 ]

Yield	Reaction Conditions	Operation in experiment
99%		To a solution of 4-pyridylcarbinol (15 g, 137.4 mmol) in DCM (200 ml) was added thionyl chloride (43.6 ml) and the resulting reaction mixture was stirred at room temperature for 4 h. The mixture was cooled to room temperature and the solvent was evaporated in vacuo. The residue was diluted with DCM and washed with a saturated solution Of NaHCO3. The combined organic layers were dried over Na2SO4 and con- centrated in vacuo to yield intermediate compound 29 (17.18 g, 99 %).
	With thionyl chloride;	(i) Reaction of <strong>[586-95-8]4-(hydroxymethyl)pyridine</strong> with thionyl chloride gives 4-(chloromethyl)pyridine which is reacted with
	With thionyl chloride; at 70℃; for 1h;	Dissolve 4-pyridinemethanol (200 mg, 1.83 mmol) in 2 ml of dichlorosulfoxide. After heating to 70 C. for 1 h, concentrate to remove dichlorosulfoxide under reduced pressure to obtain compound 39b

With thionyl chloride; at 70℃; for 1h;

Dissolve 4-pyridinemethanol (200 mg, 1.83 mmol) in 2 ml of dichlorosulfoxide. After warming to 70 C. for 1 h, concentrate to remove dichlorosulfoxide under reduced pressure to obtain compound 39b. Dissolve 39b in 5 ml of N,N- In dimethylformamide,After adding imidazole-2-carboxylic acid ethyl ester (256 mg, 1.83 mmol) and cesium carbonate (1.78 g, 5.49 mmol), the temperature was raised to 80 C. for 4 h.The reaction was detected by TLC, the reaction was stopped, cooled to room temperature, diluted with water,Extract with ethyl acetate (3×20 ml), combine the organic layers, wash with saturated brine, dry over anhydrous sodium sulfate, filter and concentrate to obtain crude product.Purified by column chromatography (DCM:MeOH=30:1) to give colorless oily liquid, ie compound1-(pyridin-4-ylmethyl)-1H-imidazole-2-carboxylic acid ethyl ester 39c (240 mg, 56.7% yield).

Reference： [1]Patent: WO2007/104783,2007,A2 .Location in patent: Page/Page column 49
[2]Phosphorus, Sulfur and Silicon and the Related Elements,1995,vol. 102,p. 45 - 50
[3]Synthetic Communications,2012,vol. 42,p. 1731 - 1745
[4]Molecules,2011,vol. 16,p. 5665 - 5673
[5]Acta Chimica Academiae Scientiarum Hungaricae,1959,vol. 19,p. 205,213
[6]Chemical and pharmaceutical bulletin,1958,vol. 6,p. 467,470
[7]Journal of the American Chemical Society,1951,vol. 73,p. 4925
[8]Journal of Medicinal Chemistry,1998,vol. 41,p. 2146 - 2163
[9]Patent: US4385058,1983,A
[10]ACS Medicinal Chemistry Letters,2013,vol. 4,p. 278 - 282
[11]Patent: CN111187218,2020,A .Location in patent: Paragraph 0227-0229
[12]Patent: CN111253317,2020,A .Location in patent: Paragraph 0228-0230

3
[ 586-95-8 ]
[ 22346-75-4 ]

Yield	Reaction Conditions	Operation in experiment
85%	With manganese tetrakis(2,6-dichlorophenyl)porphyrin; ammonium acetate; dihydrogen peroxide In dichloromethane; acetonitrile for 2h; Ambient temperature;
72%	With sodium perborate In acetic acid at 40℃;
	With water; dihydrogen peroxide; acetic acid

Reference： [1]Thellend; Battioni; Sanderson; Mansuy [Synthesis, 1997, # 12, p. 1387 - 1388]
[2]McKillop, Alexander; Kemp, Duncan [Tetrahedron, 1989, vol. 45, # 11, p. 3299 - 3306]
[3]Bixler; Niemann [Journal of Organic Chemistry, 1958, vol. 23, p. 575,580] Furukawa [Yakugaku Zasshi/Journal of the Pharmaceutical Society of Japan, 1958, vol. 78, p. 957,959][Chem.Abstr., 1959, p. 3219]

4
[ 101990-69-6 ]
[ 586-95-8 ]

Reference： [1]Journal fur praktische Chemie (Leipzig 1954),1938,vol. <2> 151,p. 65,79

6
[ 1003-67-4 ]
[ 108-24-7 ]
[ 1121-19-3 ]
[ 586-95-8 ]

Reference： [1]Journal of Medicinal Chemistry,1987,vol. 30,p. 2031 - 2046

7
[ 586-95-8 ]
[ 2304-98-5 ]
[ 21844-71-3 ]

Reference： [1]Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry,1986,vol. 25,p. 1138 - 1141

8
[ 586-95-8 ]
[ 18162-48-6 ]
[ 117423-41-3 ]

Yield	Reaction Conditions	Operation in experiment
100%	With 1H-imidazole; In DMF (N,N-dimethyl-formamide); for 3.25h;	This is a modified procedure from Hadri, A. E.; LECLERC, G. J. Heterocyclic CHEZ. 1993, 30, 631-635. To a mixture of 4- (hydroxymethyl) pyridine (7.42 g, 68.0 mmol) and imidazole (9.72 g, 142.8 mmol) in dry DMF (70 mL) was added dropwise over a 15-min period tert-butyldimethylsilyl chloride (10.76 g, 71.4) in dry DMF (30 mL). The clear solution was stirred for 3 h, poured in water (500 mL) and extracted with toluene (3 x 200 mL). The combined organic phases were dried (MGS04) and reduced to dryness affording 15.69 g (100%) a colorless oil containing little toluene. 1H NMR (400 MHz, CDC13) 8 0.10 (s, 6H) 0.94 (s, 9H) 4.73 (s, 2H) 7.24 (d, J=6.02 Hz, 1H) 8.53 (d, J=6.02 Hz, 1H).
100%	With 1H-imidazole; In N,N-dimethyl-formamide; at 20℃;	Pyridin-4-ylmethanol (2.2 g, 20 mmol) was dissolved in N,N-dimethylformamide, and tert-butyldimethylsilyl chloride (3.3 g, 22 mmol) and imidazole (2.0 g, 30 mmol were added thereto. The mixture was stirred at a room temperature overnight. After the completion of the reaction was confirmed by HPLC, water was added to the mixture, and the extraction with diethyl ether was performed 3 times. The combined organic layer was washed with a saturated saline solution and dried over magnesium sulfate, and the solvent was distilled off. Thus the title compound (4.5 g, 100%) was obtained as an oily substance. 1H-NMR (CDCl3, delta): 0.12 (6H,s), 0.96 (9H,s), 4.75 (2H,s), 7.2-7.3 (2H,m), 8.55 (2H,dd,J=1.6, 4.6 Hz)
98%	With 1H-imidazole; In dichloromethane; N,N-dimethyl-formamide; for 18h;Inert atmosphere;	To a solution of pyridin-4-ylmethanol (25.7 g, 0.24 mol) and imidazole (19.8 g, 0.29 mol) in dry DMF (300 mL) and dry DCM (33 mL) under nitrogen atmosphere was added TBDMSCl (42.6 g, 0.29 mol). The solution was stirred for 18 h under which time a precipitate formed. The reaction mixture was concentrated by removal of volatiles (about 100 mL) followed by addition of water (500 mL). The resulting mixture was extracted with 1:1 heptane:EtOAc (200 mL×3). The combined organic phases were washed with brine (×2), dried (MgSO4), filtered and evaporated to yield 4-((tert-butyldimethylsilyloxy)-methyl)pyridine (51.70 g, 98%) as an oil. 1H NMR (600 MHz, cdcl3) delta -0.01 (s, 6H), 0.82 (s, 9H), 4.63 (s, 2H), 7.14 (m, 2H), 8.43 (m, 2H).

70%	With 1H-imidazole; In dichloromethane; at 0 - 20℃; for 2h;	To a solution of compound 4-Pyridinemethanol (5 g, 45.82 mmol, 1.0 eq) and imidazole (7.97 g, 137.45 mmol, 3.0 eq) in DCM (100 mL) was added TBSCl (13.8 g, 91.64 mmol, 2.0 eq) at 0 C. The mixture was stirred at room temperature for 2 h. Then the mixture was quenched with saturated NH4Cl solution (100 mL). The mixture was extracted with ethyl acetate (50 mL×3). The combined organic phases were washed with brine, dried over anhydrous Na2SO4 and concentrated under reduced pressure. The residue was purified by silica gel chromatography to afford compound PI-59a (7.2 g, 70%).
46%	With 1H-imidazole; In N,N-dimethyl-formamide; at 20℃;	4-([ferf-Butyl(dimethyl)silyl]oxy}methyl)pyridine A mixture of pyridin-4-ylmethanol (8.0 g, 73 mmol), tert-butyldimethylsilyl chloride (14.3 g, 95 mmol) and imidazole (12.9 g, 0.19 mol) in DMF (40 ml_) was stirred overnight at room temperature. The reaction was poured onto water and extracted twice with ethyl EPO <DP n="59"/>acetate. The combined organic phases were dried (MgSO4) and evaporated under reduced pressure to yield the title compound as yellow oil (7.5 g, 46%). delta 1H-NMR (CDCI3): 8.42 (d, 2H), 7.19 (d, 2H), 4.64 (s, 2H), 0.81 (brs, 12H), 0.00 (s, 6H).
22 g (99%)	With triethylamine; In hexane; 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran;	Step A. 4-(t-Butyldimethylsilyloxy)methyl pyridine At room temperature, 10.9 g of 4-pyridylcarbinol (100 mmol) was treated with 60 mL of DCM followed by 21 mL (150 mmol) of triethylamine. After being cooled to 10 C., 18 g (120 mmol) of t-butyldimethylsilyl chloride (dissolved in 20 mL DCM) was added dropwise. The resulting reaction mixture was warmed to room temperature slowly and stirred overnight. Subsequently, it was filtered over a pad of celite, rinsed with ether. Volatiles were removed and the residue was taken up in hexane and filtered over celite again, washed with hexane/ether, and the solvents removed by rotoevaporation. This was repeated twice. Pumping under high vac of the residue thus obtained provided 22 g (99%) of the desired product as a light brown oil, mass spectrum (CI) m/e=224 (M+1)+.
	With 1H-imidazole; In N,N-dimethyl-formamide; at 20℃; for 0.5h;	Intermediate 1: N-{3-[5-(Hydroxymethyl)-3-(4-pyrimidinyl)pyrazolo[1,5-a]pyridin-2-yl]phenyl}benzamide Step A: 4-([(1,1-dimethylethyl)(dimethyl)silyl]oxy}methyl)pyridine; A solution of 4-pyridinemethanol (5.00 g, 45.8 mmol) in dry DMF (10 mL) was added Imidazole (8.42 g, 0.124 mol) and TBSCI (8.29 g, 55.0 mmol). The mixture was stirred at rt for 30 min. The reaction mixture was poured into water and extracted with diethyl ether (×2). The organic layers were combined, washed with brine, and dried (Na2SO4). The solvent was evaporated under reduced pressure. Chromatography on silica gel eluting with Hexane/EtOAc gradient (10-30% EtOAc) gave the product as a colorless oil (10.5 g).
	With 1H-imidazole; In DMF (N,N-dimethyl-formamide); at 20℃;	4-tert-Butyldimethylsilanyloxymethyl)pyridine (26B). To a solution of 4-pyridylcarbinol (26A) (40.0 g, 366.53 mmol) in 400 mL of anhydrous DMF under a nitrogen atmosphere was added imidazole (27.4 g, 403.18 mmol) and tert-butyldimethylchlorosilane (58.0 g, 384.86 mmol). The reaction was stirred overnight at room temperature. The solvent was removed in vacuo. The residue was partitioned between 750 mL EtOAc and 750 mL H2O. The layers were separated and the organic layer was washed with H2O, brine, dried over MgSO4, filtered and concentrated in vacuo to afford the title compound (26B) as a beige oil. 1H NMR (400 MHz, CDCl3) delta 8.4(m, 2H), 7.25(m, 2H), 4.74(s, 2H), 0.96 (s, 9H), 0.12(s, 6H).
	With triethylamine; In dichloromethane; at 0 - 20℃; for 4h;	To a solution of pyridin-4-ylmethanol (21.8 g, 0.20 mol) in CH2CI2 (200 mL) were added Et3N (30.0 g, 0.30 mmol) and TBSCI (45.0 g, 0.30 mmol) at 0C. The reaction mixture was stirred at room temperature for 4 h, then quenched with water. The organic phase was separated, and the aqueous layer was extracted with CH2CI2. The combined organic layers were washed with brine, dried over Na2S04 and concentrated. The residue was purified by silica gel chromatography to afford 4-((ferf-butyldimethylsilyloxy)methyl)-pyridine.[0148] A mixture of 4-((tert-butyldimethylsilyloxy)methyl)pyridin9 (8.9 g, 39.7 mmol) and O- (2,4-dinitrophenyl)hydroxylamine Y-3 (7.9 g, 39.7 mmol) in MeCN (27 ml) was stirred at 40C for 24 h, then concentrated to afford the title compound (17.1 g ), used in next step without further purification. MS (m/z): 239(M-183)+.

Reference： [1]Patent: WO2004/63156,2004,A1 .Location in patent: Page 33
[2]Patent: US2013/85127,2013,A1 .Location in patent: Paragraph 0262; 0263; 0264
[3]Journal of Organic Chemistry,2009,vol. 74,p. 3894 - 3899
[4]Patent: US2010/261755,2010,A1 .Location in patent: Page/Page column 14
[5]ACS Medicinal Chemistry Letters,2014,vol. 5,p. 538 - 543
[6]Bioorganic and Medicinal Chemistry,1997,vol. 5,p. 49 - 64
[7]Journal of Medicinal Chemistry,2014,vol. 57,p. 7577 - 7589
[8]Patent: WO2006/21449,2006,A1 .Location in patent: Page/Page column 8; 9
[9]Journal of Heterocyclic Chemistry,1993,vol. 30,p. 631 - 635
[10]Annals of Nuclear Medicine,2019,vol. 33,p. 333 - 343
[11]Patent: US2019/352288,2019,A1 .Location in patent: Paragraph 0609-0610
[12]Patent: WO2007/17096,2007,A1 .Location in patent: Page/Page column 57-58
[13]Journal of Medicinal Chemistry,1989,vol. 32,p. 2171 - 2178
[14]Patent: US5880139,1999,A
[15]Patent: US2008/51395,2008,A1 .Location in patent: Page/Page column 86
[16]Patent: US2003/229079,2003,A1 .Location in patent: Page 73
[17]Patent: WO2011/79804,2011,A1 .Location in patent: Page/Page column 43

9
[ 2459-09-8 ]
[ 586-95-8 ]
[ 26156-51-4 ]
[ 58481-17-7 ]
[ 82828-86-2 ]

Reference： [1]Bulletin of the Chemical Society of Japan,1984,vol. 57,p. 1882 - 1886

10
[ 586-95-8 ]
[ 75-91-2 ]
[ 872-85-5 ]
[ 81660-73-3 ]

Reference： [1]Journal of Organic Chemistry,1996,vol. 61,p. 1467 - 1472

11
[ 586-95-8 ]
[ 89694-35-9 ]
(2,4,5-Trioxo-3-pyridin-4-ylmethyl-imidazolidin-1-yl)-acetic acid ethyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
58%	With triphenylphosphine; diethylazodicarboxylate In tetrahydrofuran at 0℃; for 4.5h;

Reference： [1]Kotani, Takayuki; Ishii, Akira; Nagaki, Yasuhiro; Toyomaki, Yoshio; Yago, Hisashi; Suehiro, Seishi; Okukado, Nobuhisa; Okamoto, Kaoru [Chemical and Pharmaceutical Bulletin, 1997, vol. 45, # 2, p. 297 - 304]

12
[ 586-95-8 ]
[ 75-36-5 ]
[ 1007-48-3 ]

Yield	Reaction Conditions	Operation in experiment
47%	With triethylamine; In dichloromethane; at 20℃;	General procedure: To a solution of benzyl or hetero-benzyl alcohols (2.0 mmol) in CH2Cl2 (6 mL) was added acetyl chloride (173 mg, 2.2 mmol) and Et3N (202 mg, 2.0 mmol). The reaction mixture was stirred at room temperature until completion (monitored by TLC), and then water (30 mL) was added. The aqueous layer was extracted with CH2Cl2 (3 × 5 mL). The combined organic layers were washed with brine, dried over anhydrous Na2SO4, filtered, and concentrated in vacuo. The residue was puried by flash chromatography (petroleum ether/ethyl acetate 300:1 to 50:1) to give the products 5a-5l and 5q-5t.

Reference： [1]Journal of Organic Chemistry,2004,vol. 69,p. 5547 - 5554
[2]Applied Catalysis A: General,2010,vol. 382,p. 293 - 302
[3]Chemistry of Heterocyclic Compounds,1998,vol. 34,p. 40 - 43
[4]Tetrahedron Letters,2020,vol. 61
[5]Journal of the American Chemical Society,2018,vol. 140,p. 3322 - 3330

13
[ 101990-69-6 ]
palladium/barium carbonate [ No CAS ]
methanol. KOH-solution [ No CAS ]
[ 586-95-8 ]

Reference： [1]Journal fur praktische Chemie (Leipzig 1954),1938,vol. <2> 151,p. 65,79

14
[ 22346-75-4 ]
[ 108-24-7 ]
[ 64-19-7 ]
[ 586-95-8 ]

Yield	Reaction Conditions	Operation in experiment
	Hydrogenation;

Reference： [1]Jerchel et al. [Justus Liebigs Annalen der Chemie, 1958, vol. 613, p. 153,155, 162]

15
[ 22346-75-4 ]
[ 586-95-8 ]

Yield	Reaction Conditions	Operation in experiment
90%	With triphenylphosphine In methanol; dichloromethane at 23℃; for 6h;
83%	With diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate In dichloromethane at 31℃; for 16h; Sealed tube; Irradiation;
57%	With phenylsilane; 3-Methyl-1-phenyl-2-phospholene 1-oxide In acetonitrile for 16h; Irradiation; chemoselective reaction;

55%	With 4,4'-di-tert-butylbiphenyl; lithium; nickel dichloride In tetrahydrofuran at 20℃;
42%	With (4,4'-di-tert-butyl-2,2'-dipyridyl)-bis-(2-phenylpyridine(-1H))-iridium(III) hexafluorophosphate; hydrazine hydrate In dimethyl sulfoxide at 20℃; for 12h; Inert atmosphere; Irradiation; chemoselective reaction;
91 %Chromat.	With Dimethylphenylsilane In 1,4-dioxane at 30℃; for 1h; Inert atmosphere;

Reference： [1]Toganoh, Motoki; Fujino, Keitaro; Ikeda, Shinya; Furuta, Hiroyuki [Tetrahedron Letters, 2008, vol. 49, # 9, p. 1488 - 1491]
[2]Cardinale, Luana; Jacobi Von Wangelin, Axel; Konev, Mikhail O. [Organic Letters, 2020]
[3]Lecroq, William; Schleinitz, Jules; Billoue, Mallaury; Perfetto, Anna; Gaumont, Annie-Claude; Lalevée, Jacques; Ciofini, Ilaria; Grimaud, Laurence; Lakhdar, Sami [ChemPhysChem, 2021, vol. 22, # 12, p. 1237 - 1242]
[4]Alonso, Francisco; Radivoy, Gabriel; Yus, Miguel [Tetrahedron, 2000, vol. 56, # 44, p. 8673 - 8678]
[5]Kim, Kyu Dong; Lee, Jun Hee [Organic Letters, 2018, vol. 20, # 23, p. 7712 - 7716]
[6]Location in patent: experimental part Mikami, Yusuke; Noujima, Akifumi; Mitsudome, Takato; Mizugaki, Tomoo; Jitsukawa, Koichiro; Kaneda, Kiyotomi [Chemistry - A European Journal, 2011, vol. 17, # 6, p. 1768 - 1772]

16
[ 586-95-8 ]
[ 117-34-0 ]
[ 10382-20-4 ]

Yield	Reaction Conditions	Operation in experiment
58.8%	With dicyclohexyl-carbodiimide; In dichloromethane; at 20℃; for 24h;	3.4 g (16.4 mmol) of N,N'-dicyclohexylcarbodiimide (DCC) was added to a solution of 3.84 g (16.4 mmol) of diphenylacetic acid and 1.67 g (14.8 mmol) of 4-pyridylcarbinol in 50 mL of dichloromethane. The reaction mixture was stirred at room temperature for about 24 h. The urea precipitate was filtered off, and the filtrate was washed with (2 25 mL) NaHCO3 and (2 25 mL) water. The organic layer were collected and dried over MgSO4, and the solvent was evaporated yielding required compound.

Reference： [1]Journal of Organic Chemistry,2004,vol. 69,p. 5547 - 5554
[2]Dyes and Pigments,2015,vol. 112,p. 24 - 33
[3]Journal of the American Chemical Society,2005,vol. 127,p. 8000 - 8001

17
[ 586-95-8 ]
[ 98-67-9 ]
3-{5-methoxy-1-[4-(pyridin-4-ylmethoxy)-benzenesulfonyl]-1H-indol-3-yl}-propionic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		118 Synthesis of 3-{5-Methoxy-1-[4-(pyridin-4-ylmethoxy)-benzenesulfonyl]-1H-indol-3-yl}-propionic acid 145 Example 118 Synthesis of 3-{5-Methoxy-1-[4-(pyridin-4-ylmethoxy)-benzenesulfonyl]-1H-indol-3-yl}-propionic acid 145 Compound 145 can be prepared through methods described in Scheme 23, using 4-hydroxybenzenesulfonic acid and 4-pyridylcarbinol to prepare the corresponding sulfonyl chloride. The various coupling of the sulfonyl chloride to 5-methoxy-indole-3-p;ropionic ester or the corresponding acid as described in Scheme 7, 10, or 12.

Reference： [1]Current Patent Assignee: DAIICHI SANKYO COMPANY, LIMITED - US2005/288354, 2005, A1

18
[ 586-95-8 ]
[ 111726-46-6 ]
[ 191873-50-4 ]

Reference： [1]Synthetic Communications,2007,vol. 37,p. 3367 - 3379
[2]Journal of Heterocyclic Chemistry,2011,vol. 48,p. 1238 - 1242

19
[ 586-95-8 ]
[ 1822-53-3 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: DEAD, PPh₃ / tetrahydrofuran / Ambient temperature 2: NaOH / methanol

Reference： [1]Deziel; Malenfant [Bioorganic and Medicinal Chemistry Letters, 1998, vol. 8, # 11, p. 1437 - 1442]

20
[ 586-95-8 ]
[ 70199-60-9 ]

Reference： [1]Chemistry of Heterocyclic Compounds,1998,vol. 34,p. 40 - 43

21
[ 586-95-8 ]
[ 152121-47-6 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 4 steps 1: 97 percent / imidazole / dimethylformamide / 18 h / Ambient temperature 2: 1.) LDA / 1.) THF, hexane, -20 deg C, 45 min, 2.) THF, hexane, from -20 deg C to RT, 2.5 h 3: 44 percent / NH₄OAc, Cu(OAc)2*H₂O, CH₃CO₂H / 0.67 h / 98 °C 4: 78 percent / aq. K₂S₂O₈, CH₃CO₂H / 18 h

Reference： [1]Gallagher, Timothy F.; Seibel, George L.; Kassis, Shouki; Laydon, Jeffrey T.; Blumenthal, Mary Jane; Lee, John C.; Lee, Dennis; Boehm, Jeffrey C.; Fier-Thompson, Susan M.; Abt, Jeffrey W.; Soreson, Margaret E.; Smietana, Juanita M.; Hall, Ralph F.; Garigipati, Ravi S.; Bender, Paul E.; Erhard, Karl F.; Krog, Arnold J.; Hofmann, Glenn A.; Sheldrake, Peter L.; McDonnell, Peter C.; Kumar, Sanjay; Young, Peter R.; Adams, Jerry L. [Bioorganic and Medicinal Chemistry, 1997, vol. 5, # 1, p. 49 - 64]

22
[ 586-95-8 ]
[ 152121-53-4 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: 97 percent / imidazole / dimethylformamide / 18 h / Ambient temperature 2: 1.) LDA / 1.) THF, hexane, -20 deg C, 45 min, 2.) THF, hexane, from -20 deg C to RT, 2.5 h 3: NH₄OAc, Cu(OAc)2*H₂O, CH₃CO₂H / 0.67 h / 98 °C

23
[ 586-95-8 ]
[ 77047-42-8 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 83 percent / SOCl₂ / 3 h / Heating 2: 1.) Na / 1.) C₆H₆, reflux, 30 min, 2.) C₆H₆, 30 min
	Multi-step reaction with 2 steps 1: Ph₃PBr₂ / CH₂Cl₂ / 1) 0 deg C, 15 min, 2) rt, 1 h 2: 1) NaH / 1) THF, hexane, rt, 2 h, 2) THF, rt, overnight
	Multi-step reaction with 2 steps 1: thionyl chloride / dichloromethane / 3 h / 0 °C / Reflux 2: sodium hydride / tetrahydrofuran

Reference： [1]Kaushik, Mahabir P.; Vaidyanathaswamy, Ramamoorthy [Phosphorus, Sulfur and Silicon and the Related Elements, 1995, vol. 102, # 1-4, p. 45 - 50]
[2]Ornstein, Paul L.; Schaus, John M.; Chambers, John W.; Huser, Diane L.; Leander, J. David; et al. [Journal of Medicinal Chemistry, 1989, vol. 32, # 4, p. 827 - 833]
[3]Xue, Jian; Diao, Jiasheng; Cai, Guobin; Deng, Lisheng; Zheng, Baisong; Yao, Yuan; Song, Yongcheng [ACS Medicinal Chemistry Letters, 2013, vol. 4, # 2, p. 278 - 282]

24
[ 586-95-8 ]
[ 59663-96-6 ]

Reference： [1]Journal of Heterocyclic Chemistry,1993,vol. 30,p. 631 - 635
[2]Journal of Medicinal Chemistry,1989,vol. 32,p. 2171 - 2178

25
[ 586-95-8 ]
[ 17973-86-3 ]
[ 325781-41-7 ]

Yield	Reaction Conditions	Operation in experiment
71%	With sodium hydride; In tetrahydrofuran; at 0 - 50℃; for 6h;	Example 21: Preparation of 1-(4-chlorophenylamino)-4-(4-pyridylmethoxy)pyridazine [51.2] Step 1: To a mixture of 3,6- dibromo-pyridazine (500 mg, 2.10mmol, for preparation see Pwdrali et al.; J.Org. Chem.; 23, 1958; 778) and 4-pyridylcarbinol (229 mg. 2.10 mmol) in anhydrous tetrahydronfuran (10 mL) at 0 C under argon was added sodium hydride (302 mg, 12.6 mmol). The reaction mixture was warmed up to RT and then was stirred at 50 C under argon for 6h. After cooled to 0 C, the resultant orange mixture was diluted with ethyl acetate (20 mL) and then excess sodium hydride was quenched by water until no bubble occurred. The organic layer was collected and washed by brine ( 3 x 10 mL) and dried over anhydrous Na2SO4, filtered, and evaporated in vacuo, which afforded 400 mg (1.50 mmol, 71% yield) of 1-bromo-4-(4-pyridylmethoxy)pyridazine as an oil. The crude product was pure enough to carried out next step reaction without further purification. 1H-NMR (MeOH-d4) 8.52-8.54 (m, 2H), 7.80 (d, 1H), 7.52-7.54 (m, 2H), 7.25 (d, 1H), 5.60 (s, 2H); MS LC 266 M+,269 (M+3H)+, cacl. 266; TLC (3:2 v/v ethyl acetate-hexanes) Rf= 0.20.
71%	With sodium hydride; In tetrahydrofuran; at 0 - 50℃; for 6h;	Step 1: To a mixture of <strong>[17973-86-3]3,6-dibromo-pyridazine</strong> (500 mg, 2.10 mmol, for preparation see Pwdrali et al.; J. Org. Chem.; 23, 1958; 778) and 4-pyridylcarbinol (229 mg. 2.10 mmol) in anhydrous tetrahydronfuran (10 mL) at 0 C. under argon was added sodium hydride (302 mg, 12.6 mmol). The reaction mixture was warmed up to RT and then was stirred at 50 C. under argon for 6 h. After cooled to 0 C., the resultant orange mixture was diluted with ethyl acetate (20 mL) and then excess sodium hydride was quenched by water until no bubble occurred. The organic layer was collected and washed by brine (3×10 mL) and dried over anhydrous Na2SO4, filtered, and evaporated in vacuo, which afforded 400 mg (1.50 mmol, 71% yield) of 1-bromo-4-(4-pyridylmethoxy)pyridazine as an oil. The crude product was pure enough to carried out next step reaction without further purification. 1H-NMR (MeOH-d4) 8.52-8.54 (m, 2H), 7.80 (d, 1H), 7.52-7.54 (m, 2H), 7.25 (d, 1H), 5.60 (s, 2H); MS LC 266 M+, 269 (M+3H)+, cacl. 266; TLC (3:2 v/v ethyl acetate-hexanes) Rf=0.20.

Reference： [1]Patent: EP1208096,2004,B1 .Location in patent: Page 37
[2]Patent: US6903101,2005,B1 .Location in patent: Page/Page column 48

26
[ 586-95-8 ]
[ 1822-51-1 ]

Yield	Reaction Conditions	Operation in experiment
100%	With thionyl chloride; In acetonitrile; at 50℃; for 1h;	4-Chloromethylpyridine Hydrochloride (21); EMI35.0[0161] <strong>[586-95-8]4-Hydroxymethylpyridine</strong> (20) (54.4 g, 0.50 mol) was dissolved in acetonitrile 202 ml. The solution was added dropwise to a mixture of thionyl chloride (65.3 g, 0.55 mol) and acetonitrile (109 ml) under 50[deg.] C. The mixture was stirred at the same temperature for 1 hour, then cooled to room temperature to yield a slurry (quantitative) of the objective (21). [0162] <1>H-NMR (DMSO-TMS) [delta] ppm: 5.09 (s, 2H), 8.09 (d, J=6.6 Hz, 2H), 8.94 (d, J=6.6 Hz, 2H).
	With thionyl chloride; In acetonitrile;	(IV) 4-Chloromethylpyridine hydrochloride (19) STR16 <strong>[586-95-8]4-Hydroxymethylpyridine</strong> (18) 54.4 g (0.50 mol) was dissolved in acetonitrile 202 ml. The solution was added dropwise to the mixture of thionyl chloride 65.3 g (0.55 mol) and acetonitrile 109 ml under 50 C. The mixture was stirred at the same temperature for 1 hour, then cooled to room temperature to yield the slurry (quantitative) of the objective (19). 1 H-NMR (DMSO-TMS) delta ppm: 5.09 (s, 2H), 8.09 (d, J=6.6 Hz, 2H), 8.94 (d, J=6.6 Hz, 2H),
26.9 g	With thionyl chloride; In methanol;	(4) 4-pyridine methanol was reacted with thionyl chloride (26.18 g, 0.22 mol) in methanol solution, and traced by thin layer chromatography. After the reaction was completely converted to 4-chloromethylpyridine hydrochloride, the reaction was stopped. After suction filtration, the product was obtained in a yield of 26.9 g (yield: yield)

Reference： [1]Patent: US2003/195363,2003,A1 .Location in patent: Page/Page column 13
[2]Patent: US6057448,2000,A
[3]ChemMedChem,2015,vol. 10,p. 1875 - 1883
[4]Patent: CN109761888,2019,A .Location in patent: Paragraph 0016; 0019; 0023; 0024; 0028; 0029; 0033

27
[ 586-95-8 ]
[ 100-39-0 ]
[ 158984-76-0 ]

Yield	Reaction Conditions	Operation in experiment
64%		(l-Benzyl-l,2,3,6-tetrahydropyridin-4-yl)methanol. 4-Hydroxymethyl- pyridine (20 g, 183 mmol, 1.0 eq) was dissolved in DMF (80 mL) andbenzylbromide (24.2 mL; 202 mmol) was added and the solution was stirred at 100 C for 2 hours. The solution was allowed to cool to RT and diluted with EtOH (300 mL) and treated portionwise with NaBH4 (8.7 g; 230 mmol) and stirred at reflux for 3 hours. The solution was allowed to cool to RT and concentrated largely. The residue was taken up in EtOAc and water and the organic phase was dried (Na2S04), filtered and concentrated to give 35 g crude oil. The material was purified with a short plug (10 cm) of silica eluting with EtOAc to give the product (23.9 g; 64%) which was isolated as an oil. NMR (300 MHz, CDC13) delta ppm 7.39-7.2 (m, 5H), 5.69-5.63 (m, 1H), 4.03 (s, 2H), 3.58 (s, 2H), 3.0 (m, 2H), 2.6 (t, J= 6 Hz, 2H), 2.21-2.11 (m, 2H).
64%		4-(Hydroxymethyl)pyridine (20 g, 183 mmol) was dissolved in DMF (80 ml), benzyl bromide (24.2 ml, 202 mmol) was added and the magnetically stirred solution was heated at 100 C for 2 hours. The solution was successively allowed to cool to room temperature, diluted with EtOH (300 mL), treated portion wise with NaBH4 (8.7 g, 230 mmol) and stirred at reflux temperature for 3 hours. The resulting solution was allowed to cool to room temperature and concentrated in vacuo. The residue was taken up in EtOAc and water. After separation of the layers, the organic phase was dried (Na2SO4), filtered and concentrated to give 35 g of a crude oil. The material was purified with a short column (10 cm) of silica gel (EtOAc) to give 37 (23.9 g, 64%) as an oil. 1H NMR (300 MHz, CDCl3) delta 7.39-7.20 (m, 5H), 5.69-5.63 (m, 1H), 4.03 (s, 2H), 3.58 (s, 2H), 3.00 (m, 2H), 2.60 (t, J = 6 Hz, 2H), 2.21-2.11 (m, 2H).
	With sodium tetrahydroborate; In N-methyl-acetamide; ethanol;	a) 10.7 ml (0.0901 mol) of benzyl bromide were added to a solution of 8.9 g (0.0815 mol) of 4-hydroxymethylpyridine in 30 ml of dimethylformamide and the mixture was stirred at 100 for 2 hours. Subsequently, the reaction mixture was cooled to room temperature, diluted with 111 ml of ethanol and treated portion-wise with 3.9 g (0.103 mol) of NaBH4. The mixture was boiled under reflux for 3 hours and stirred at room temperature for a further 18 hours. Then, the solvent was distilled off, the residue was partitioned between dichloromethane/water, extracted and dried. After removal of the solvent the residue was chromatographed on silica gel with ethyl acetate/hexane 1:1 as the eluent. 9.26 g (56%) of (1-benzyl-1,2,3,6-tetrahydro-pyridin-4-yl)-methanol were obtained as yellow crystals; m.p. 57-60.

	With sodium borohydrid; In N-methyl-acetamide;	Step 1 1-Benzyl-4-hydroxymethyl-1,2,3,6-tetrahydropyridine A solution of 4-hydroxymethylpyridine (20 g, 0.183 mol) in anhydrous dimethylformamide (70 ml) was treated with benzyl bromide (24 ml, 0.202 mol) and the mixture was stirred at 100 C. for two hours. The reaction was cooled to room temperature and diluted with absolute ethanol (250 ml). Sodium borohydride (8.7 g, 0.229 mol) was added portionwise and the mixture stirred at reflux for 3 hours. The solvent was evaporated in vacuo and the residue partitioned between dichloromethane and water. The organic phase was separated, dried (MgSO4) and evaporated in vacuo. The residue was chromatographed with 1:1 hexane/ethyl acetate as eluant to the title compound (13 g, 35%) as a lemon yellow solid; deltaH (CDCl3) 2.12-2.20 (2H, m, tetrahydropyridinyl CH2), 2.60 (2H, t, J 7.5 Hz, tetrahydropyridinyl CH2), 2.96-3.04 (2H, m, tetrahydropyridyl CH2), 3.60 (2H, s, PhCH2 N), 4.00-4.04 (2H, m, CH2 OH), 5.60-5.66 (1H, m, tetrahydropyridinyl 5-H), and 7.20-7.40 (5H, m, ArH). m/z (CI+, NH3) 204 (M+1)+.
		(i) (a) Benzyl bromide, D F, 100C, 3h, (b) NaBH4, EtOH, 70-80C, 2h. (Ref.for Step-(i): WO2012004378)

Reference： [1]Patent: WO2012/4378,2012,A1 .Location in patent: Page/Page column 37
[2]Bioorganic and Medicinal Chemistry Letters,2018,vol. 28,p. 459 - 465
[3]Patent: US5688798,1997,A
[4]Patent: US5700809,1997,A
[5]Patent: WO2013/80222,2013,A1 .Location in patent: Page/Page column 33

28
[ 586-95-8 ]
[ 54326-16-8 ]
[ 4909-78-8 ]
5-Chloro-1-(pyrid-4-ylmethyl)pyrimidin-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	In N,N-dimethyl-formamide;	EXAMPLE 14 5-Chloro-1-(pyrid-4-ylmethyl)pyrimidin-2-one N,N-Dimethylformamide dineopentyl acetal (1.8 ml) was added to a stirred suspension of <strong>[54326-16-8]5-chloropyrimidin-2-one</strong> (522 mg) and 4-pyridylcarbinol (611 mg) in dry N,N-dimethylformamide (10 ml) under nitrogen and the the mixture was then heated at 90 C. After 41/2 h the reaction mixture was evaporated to a brown solid which was subjected to column chromatography on silica developing and eluding with chloroform-ethanol, 14:1. This gave a yellow crystalline solid which was subjected to p.l.c. on silica developing with chloroform-ethanol, 9:1 (three runs). The major band was eluted with chloroform-ethanol, 1:1, to give a pale yellow foam which was crystallized from acetone to give off white crystals of the title pyrimidinone (210 mg), m.p. 205-206 C., lambdamax (EtOH) 246 nm (epsilon 7.050), 332.5 nm (epsilon 950).

Reference： [1]Patent: US4399140,1983,A

29
[ 586-95-8 ]
DBU (1,8-diazabicyclo[4.3.0]undec-7-ene) [ No CAS ]
[ 2393-17-1 ]
[ 530-62-1 ]
(4-pyridylmethyl) (4-hydroxycarbonylethylphenyl)carbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine; In tetrahydrofuran; hydrogenchloride;	Example 64 (4-Pyridylmethyl) {4-[(4,5-dimethoxy-2-ethoxycarbonylphenyl)-aminocarbonylethyl]phenyl) carbamate 0.32 g of 1,1-carbonyldiimidazole was dissolved in 3 ml of tetrahydrofuran (THF). 0.22 g of 4-pyridinemethanol was then added thereto and the mixture was stirred at room temperature for 1 hour. 0.35 g of 4-aminohydrocinnamic acid, 0.60 g of DBU (1,8-diazabicyclo[4.3.0]undec-7-ene), and 0.5 ml of triethylamine were added to 10 ml of tetrahydrofuran, followed by stirring at room temperature for 1 hour. The former solution was added to the latter solution and the obtained mixture was stirred in that state for 18 hours. The solvent was removed by distillation under reduced pressure. The residue was poured into water and adjusted to pH 6 with the aid of IN hydrochloric acid. The precipitated solid was separated by filtration and subjected to vacuum drying. Thus, 0.08 g of (4-pyridylmethyl) (4-hydroxycarbonylethylphenyl)carbamate was obtained as a pink solid.

Reference： [1]Patent: EP1229010,2002,A1

30
[ 586-95-8 ]
[ 3943-74-6 ]
[ 953723-52-9 ]

Yield	Reaction Conditions	Operation in experiment
80%	With triphenylphosphine; diethylazodicarboxylate In tetrahydrofuran at 0 - 20℃; for 1h;	48.A To a solution of methyl vanillate (182 mg; 1.00 mmol) in THF (10 mL), were added 4-pyridinemethanol (141 mg; 1.30 mmol) and triphenylphosphine (341 mg; 1.30 mmol). After the solution was cooled at O0C, diethyl azodicarboxylate (206 uL; 1.30 mmol) was added dropwise. Then the cooling bath was removed and the reaction was allowed to warm to room temperature and stirred for 1 hour. The solvent was removed under vacuum. The crude mixture was partially purified by ion-exchange chromatography [SCX, DCM/MeOH (1/1) to MeOHZNH4OH (9/1)]. The resulting compound was further purified by column chromatography [SiO2, Petroleum ether/EtOAc (8/2 to 6/4)] to furnish the title compound (220 mg; 80% yield).LCMS (RT): 0.89 min (Method D); MS (ES+) gave m/z: 274.0 (MH+).

Reference： [1]Current Patent Assignee: NIKEM RESEARCH; ADDEX THERAPEUTICS SA - WO2008/117175, 2008, A2 Location in patent: Page/Page column 118

31
[ 586-95-8 ]
[ 348-36-7 ]
[ 921039-96-5 ]

Yield	Reaction Conditions	Operation in experiment
	With tributylphosphine; 1,1'-azodicarbonyl-dipiperidine; In toluene; at 20℃; for 48h;	1.1. ethyl 5-fluoro-1-[(pyridin-4-yl)methyl]-1H-indole-2-carboxylate A solution of 5.5 g (21.72 mmol) of 1,1'-azodicarbonyl-dipiperidine, in solution in 15 ml of dry toluene, is added, under argon at 20° C., dropwise, to a solution of 3 g (14.48 mmol) of <strong>[348-36-7]ethyl 5-fluoro-1H-indole-2-carboxylate</strong>, 2.37 g (21.72 mmol) of 4-pyridylcarbinol and 5.45 ml (21.72 mmol) of n-tributylphosphine in 200 ml of toluene. The mixture is stirred at 20° C. for 48 h. The reaction mixture is subsequently concentrated under reduced pressure. The residue is purified by silica column chromatography (eluent: heptane/ethyl acetate). 3.2 g of the expected product are thus isolated, which product is used as it is in the subsequent synthesis.

Reference： [1]Patent: US2009/42873,2009,A1 .Location in patent: Page/Page column 19

32
[ 221675-35-0 ]
[ 586-95-8 ]
[ 1041261-44-2 ]

Yield	Reaction Conditions	Operation in experiment
	With triphenylphosphine; diethylazodicarboxylate; In tetrahydrofuran; at 0 - 20℃;Inert atmosphere;	3.3 ethyl 1-[(4-pyridyl)methyl]-1H-pyrrolo[2,3-b]pyridine-2-carboxylate; 0.51 g (4.73 mmol) of 4-pyridylmethanol and then 1.24 g (4.73 mmol) of triphenyl-phosphine are successively added with stirring to a solution of 0.6 g (3.15 mmol) of <strong>[221675-35-0]ethyl 1H-pyrrolo[2,3-b]pyridine-2-carboxylate</strong>, obtained according to the protocol described in step 3.2, in 40 mL of dry tetrahydrofuran, maintained under an inert atmosphere. 0.82 g (4.73 mmol) of diethyl azodicarboxylate is then added dropwise at 0 C. The reaction mixture is stirred for 24 hours at room temperature and then concentrated under reduced pressure. A mixture of water and ethyl acetate (20 mL, v/v) is added and the pH of the reaction mixture is adjusted to 5-6 by adding acetic acid. The organic phase separated out is then washed twice with 10 mL of water and once with 10 mL of saturated sodium chloride solution and then dried over magnesium sulfate. After concentrating under reduced pressure, the resulting oil is purified by chromatography on a column of silica gel. 0.66 g of expected product is isolated.1H NMR (CDCl3), delta (ppm): 8.5 (m, 3H); 8.1 (dd, 1H); 7.35 (s, 1H); 7.2 (m, 1H); 7.0 (d, 2H); 6.0 (s, 2H); 4.3 (q, 2H); 1.3 (t, 3H).

Reference： [1]Patent: US2009/298865,2009,A1 .Location in patent: Page/Page column 7

33
[ 586-95-8 ]
[ 74-88-4 ]
[ 6457-57-4 ]

Yield	Reaction Conditions	Operation in experiment
95%	In methanol at 20℃; for 4h; Reflux;
92%	In methanol at 75℃; Inert atmosphere; Darkness;
82%	In acetone

Reference： [1]Edson, Joseph B.; Spencer, Liam P.; Boncella, James M. [Organic Letters, 2011, vol. 13, # 23, p. 6156 - 6159]
[2]Cailotto, Simone; Negrato, Matteo; Daniele, Salvatore; Luque, Rafael; Selva, Maurizio; Amadio, Emanuele; Perosa, Alvise [Green Chemistry, 2020, vol. 22, # 4, p. 1145 - 1149]
[3]Location in patent: scheme or table Jun, Daniel; Paar, Martin; Binder, Jiri; Marek, Jan; Pohanka, Miroslav; Stodulka, Petr; Kuca, Kamil [Letters in Organic Chemistry, 2009, vol. 6, # 6, p. 500 - 503]

34
[ 586-95-8 ]
[ 13958-98-0 ]
[ 927806-61-9 ]

Yield	Reaction Conditions	Operation in experiment
		Step A: Preparation of 2-(pyridin-4-yl)furo[2,3-c]pyridin-3-amine: To a cold (0 C.) suspension of NaH (60% dispersion in mineral oil, 0.053 g, 1.31 mmol) in DMF (2.0 mL) was added a solution of pyridin-4-ylmethanol (0.131, 1.20 mmol) in DMF (2.0 mL) dropwise. The reaction mixture was stirred for 10 minutes, and then a solution of 3-bromoisonicotinoitrile (0.200 g, 1.09 mmol) in DMF (5.0 mL) was added dropwise. The reaction mixture was stirred for 1 hour at room temperature before quenching with water (20 mL). The aqueous layer was extracted with ethyl acetate (3×50 mL). The combined organic layers were dried, filtered and concentrated. The crude product was purified by flash column chromatography, eluting with CH2Cl2/MeOH (20:1) and CH2Cl2/MeOH (100:7) to give 0.070 g of the desired product as a yellow solid. MS (APCI) m/z 212.5 (M+1):

Reference： [1]Patent: US2007/49603,2007,A1 .Location in patent: Page/Page column 49-50

35
[ 586-95-8 ]
[ 65737-59-9 ]

Reference： [1]Chemical Communications,2011,vol. 47,p. 1482 - 1484
[2]Journal of the American Chemical Society,2018,vol. 140,p. 3322 - 3330

36
[ 586-95-8 ]
[ 1152841-31-0 ]

Reference： [1]Patent: WO2011/71725,2011,A1
[2]Patent: WO2011/71716,2011,A1

37
[ 586-95-8 ]
[ 474432-56-9 ]

Reference： [1]Patent: WO2011/79804,2011,A1
[2]Patent: US2012/245178,2012,A1
[3]Journal of Medicinal Chemistry,2014,vol. 57,p. 7577 - 7589
[4]Patent: WO2015/66371,2015,A1

38
[ 586-95-8 ]
[ 474432-57-0 ]

Reference： [1]Patent: WO2011/79804,2011,A1
[2]Patent: US2012/245178,2012,A1
[3]Journal of Medicinal Chemistry,2014,vol. 57,p. 7577 - 7589
[4]Patent: WO2015/66371,2015,A1

39
[ 586-95-8 ]
[ 50824-04-9 ]
[ 1245014-56-5 ]

Yield	Reaction Conditions	Operation in experiment
	With di-isopropyl azodicarboxylate; triphenylphosphine; In 1,4-dioxane; at 20℃; for 18h;	To a suspension of <strong>[50824-04-9]4-bromo-2-(trifluoromethyl)phenol</strong> (8.00 g) in 1 ,4-dioxane (100 ml), triphenylphosphine (10.99 g) and 4-pyridylcarbinol (3.84 g) were added. Then diisopropyl azodicarboxylate (8.93 g) was dropwised and stirred at 20 C for 18h. The mixture was evaporated off the solvent, diethyl ether (100ml) and /so- hexane (25ml) were added and stirred at 20 C for 2h, stood for 3 days, filtered and washed with diethyl ether and /'so-hexane. The filtrate was concentrated and purified by Biotage SNAP cartridge KP-Sil column (100g, heptane:ethyl acetate=1 :0, 2:1 to 1 : 1 ) to give 1 1.16g red-orange oil as 4-((4-bromo-2-(trifluoromethyl)phenoxy)methyl)- pyridine (80 % purity).1H NMR (CDCI3)5: 8.64 (d, 2H, J=6.0Hz), 7.74 (d, 1 H, J=2.4Hz), 7.59 (dd, 1 H, J=8.8,2.4Hz), 7.35 (d, 2H, J=5.9Hz), 6.87 (d, 1 H, J=8.8Hz), 5.17 (s, 2H).

Reference： [1]Patent: WO2011/86125,2011,A1 .Location in patent: Page/Page column 51

40
[ 586-95-8 ]
[ 185346-79-6 ]
[ 1372147-57-3 ]

Yield	Reaction Conditions	Operation in experiment
83%	Stage #1: pyridine-4-methanol With sodium hydride In 1-methyl-pyrrolidin-2-one; mineral oil at 60℃; for 0.5h; Cooling with ice; Stage #2: 4-(benzyloxy)-1-bromo-2-fluorobenzene In 1-methyl-pyrrolidin-2-one; mineral oil at 100℃; for 2h;	General procedure II for the S_NAr reaction General procedure: A solution of 4-pyridinemethanol (1.15 equiv) in NMP was added dropwise (30 min) to a suspension of NaH (60% dispersion in mineral oil, 1.10 equiv) in NMP cooled with an ice bath. After the end of the addition, the reaction mixture was heated to 60 °C for 30 min. Then, a solution of 7 (1.00 equiv) in NMP was added dropwise. After the end of the addition (20 min), the reaction mixture was heated to 100 °C for 2 hours. The black mixture was cooled and poured into ice-water. After 2 hours of stirring, the suspension was collected by filtration and washed with water. The residue was purified by flash column chromatography.

Reference： [1]Leflemme, Nicolas; Stoit, Axel R.; Borghese, Alfio [Tetrahedron Letters, 2012, vol. 53, # 19, p. 2432 - 2435]

41
[ 586-95-8 ]
[ 5157-75-5 ]
[ 1407229-62-2 ]

Yield	Reaction Conditions	Operation in experiment
55%	With triethylamine In tetrahydrofuran for 22h;

Reference： [1]Łêska, Bogusława; Schroeder, Grzegorz; Pankiewicz, Radosław; Mikisz, Bogusława [Journal of Molecular Structure, 2012, vol. 1027, p. 116 - 123]

42
[ 586-95-8 ]
[ 71935-32-5 ]

Reference： [1]Patent: US2013/85127,2013,A1

43
[ 586-95-8 ]
[ 1453-82-3 ]

Yield	Reaction Conditions	Operation in experiment
95%	With tert.-butylhydroperoxide; ammonium hydroxide In water at 100℃; for 16h;
93%	With tert.-butylhydroperoxide; ammonia; oxygen In water; N,N-dimethyl-formamide at 80℃; for 5h; Green chemistry;

Reference： [1]Wu, Xiao-Feng; Sharif, Muhammad; Feng, Jian-Bo; Neumann, Helfried; Pews-Davtyan, Anahit; Langer, Peter; Beller, Matthias [Green Chemistry, 2013, vol. 15, # 7, p. 1956 - 1961]
[2]Molla, Rostam Ali; Ghosh, Kajari; Tuhina; Manirul Islam [New Journal of Chemistry, 2015, vol. 39, # 2, p. 921 - 930]

44
[ 586-95-8 ]
[ 98-86-2 ]
[ 36939-02-3 ]

Yield	Reaction Conditions	Operation in experiment
86%	With P,P'-1,2-bis(diphenylphosphino)ethane(P,N-diphenyl(o-N-methylanilido)phosphine)rhodium(I); caesium carbonate; In 5,5-dimethyl-1,3-cyclohexadiene; for 24h;Inert atmosphere; Schlenk technique;	General procedure: A solution of catalyst 1 (2 mol %, 0.01 mmol), acetophenone (1.0 mmol), benzyl alcohol (1.2 mmol), cesium carbonate (1.5 mmol), and xylene (3 mL) were stirred in a Schlenk tube in N2 atmosphere. The mixture was heated under reflux for 24 h and then cooled to room temperature. The resulting solution was directly purified by column chromatography with petroleum ether/ethyl acetate (10 : 1) as eluent to give the desired product.
83%	With C38H43IrN2PS2(1+)*CF3O3S(1-); caesium carbonate; In tert-Amyl alcohol; at 120℃; for 24h;Schlenk technique; Inert atmosphere;	General procedure: Catalyst 2b (1 mol%, 0.01 mmol), benzylalcohol (1.1 mmol), acetophenone (1.0 mmol), Cesiumcarbonate (1.0 mmol), and tert-amyl alcohol (2 mL) was added toa Schlenk tube under N2 atmosphere. The mixture was heated under 120oC for 24 h and then cooled to room temperature. Theresulting solution was directly purified by columnchromatography with petroleum ether/ethyl acetate (10:1) as eluent to give 1,3-diphenylpropan-1-one (5a) as awhite solid.
70%	With [ruthenium(II)(eta6-1-methyl-4-isopropyl-benzene)(chloride)(mu-chloride)]2; potassium tert-butylate; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene; In tert-Amyl alcohol; at 120℃; for 16h;Inert atmosphere; Schlenk technique;	General procedure: t-BuOK (0.4 mmol, 44.8 mg), Xantphos (0.01 mmol, 5.8 mg) and [RuCl2(p-cymene)]2 (0.005 mmol, 3.2 mg) were added in a Schlenk tube, then 3-(Hydroxymethyl)pyridine 1a (1.2 mmol, 130 mg), acetophenone 2a (1 mmol, 120 mg) were dissolved in tert-amyl alcohol (1 mL), and the resulting liquid mixture was added to the Schlenk tube under N2 atmosphere. The Schlenk tube was closed and stirred at 120 C for 16 h. After cooling down to room temperature, the reaction mixture was filtered, then it was purified by preparative TLC on silica, eluting with petroleum ether (60-90 C): ethyl acetate (3:1) to give 3-(3-Pyridinyl)-1-phenylpropan-1-one 3a as a white solid (164 mg, 78%).

Reference： [1]Russian Journal of General Chemistry,2016,vol. 86,p. 178 - 183
Zh. Obshch. Khim.,
[2]Tetrahedron Letters,2014,vol. 55,p. 7233 - 7235
[3]Organic Letters,2017,vol. 19,p. 1080 - 1083
[4]Tetrahedron,2014,vol. 70,p. 1193 - 1198

45
[ 586-95-8 ]
[ 14401-51-5 ]
[ 1596320-86-3 ]

Yield	Reaction Conditions	Operation in experiment
63%	With mu-diiodo-di((eta5-pentamethylcyclopentadienyl)(iodo)iridium); caesium carbonate; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene; In 1,4-dioxane; at 20 - 110℃; for 20h;	General procedure: [Cp*IrI2]2 (1 mol %, 0.01 mmol), xantphos (2 mol %,0.02 mmol) and dioxane (2 mL) were stirred shortly in a Schlenk tube at room temperature. Subsequently, 3-pyridinemethanol (2.0 mmol), benzamidine hydrochloride(1.0 mmol), and cesium carbonate (1.0 mmol)were added. The mixture was heated under 110C for 20 h and then cooled down to room temperature. The resulting solution was purified by column chromatography with petroleum ether-ethyl acetate(10 : 1) as an eluent to give 2,4-diphenyl-6-(pyridin-3-yl)-1,3,5-triazine (3a) as a white solid.

Reference： [1]Organic and Biomolecular Chemistry,2014,vol. 12,p. 2761 - 2768
[2]Russian Journal of General Chemistry,2016,vol. 86,p. 380 - 386
Zh. Obshch. Khim.,2016,vol. 86,p. 380 - 386,7

46
[ 586-95-8 ]
[ 1805789-54-1 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 10 steps 1.1: acetonitrile / 3 h / Reflux 1.2: 0.5 h / -35 - -20 °C 2.1: borane-THF / tetrahydrofuran / -30 - 20 °C 2.2: 4 h / Reflux 3.1: 10% Pd/C; hydrogen / methanol / 50 °C 3.2: 48 h / 0 °C 4.1: sodium azide / N,N-dimethyl-formamide / 60 °C 5.1: 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; dmap / dichloromethane / 16 h 6.1: lithium hydroxide hydrate / methanol; tetrahydrofuran; water / 2 h 7.1: N-ethyl-N,N-diisopropylamine / dichloromethane / 14 h / 0 - 20 °C 8.1: 15% Pd/C; hydrogen / methanol / 1.5 h 9.1: tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate / toluene / 0.08 h 9.2: 16 h / 95 °C 10.1: hydrogenchloride / methanol / 3 h / 20 °C

Reference： [1]Current Patent Assignee: CANCER RESEARCH UK - WO2015/124941, 2015, A1

47
[ 586-95-8 ]
[ 69583-00-2 ]

Reference： [1]ChemMedChem,2015,vol. 10,p. 1875 - 1883

48
[ 586-95-8 ]
[ 1985605-59-1 ]
[ 1985606-20-9 ]

Yield	Reaction Conditions	Operation in experiment
35%	With diethylazodicarboxylate In dichloromethane; toluene at 20℃; for 0.5h;	10 Compound III-2 (150mg, 0.31mmol) in dichloromethane (2mL) solution of, at room temperature, polymer-supported triphenylphosphine 3mmol / g (310mg, 0.93mmol), pyridine-4-yl methanol (68mg, 0.62mol), DEAD 40% toluene solution (270 mg, 0.62 mmol) was added, It was stirred at room temperature for 30 minutes. The reaction solution Amino column chromatography (ethyl acetate - methanol) to give the compound II-143 (63mg, 35% yield).
35%	With triphenylphosphine; diethylazodicarboxylate In dichloromethane; toluene at 20℃; for 0.5h;	16 Example 16 Production method of compound II-143 Compound III-2 (150 mg, 0.31 mmol) in dichloromethane(2 mL) were added dropwise 3 mmol / g (310 mg, 0.93 mmol) of polymer-supported triphenylphosphine, pyridin-4-ylmethanol(68 mg, 0.62 mmol), DEAD 40% toluene solution(270 mg, 0.62 mmol), and the mixture was stirred at room temperature for 30 minutes.The reaction solution was subjected to amino column chromatography (ethyl acetate-methanol)To give compound II-143 (63 mg, yield 35%).
35%	With triphenylphosphine; diethylazodicarboxylate In dichloromethane; toluene at 20℃; for 0.5h;	8 Example 8 To a solution of Compound III-1 (150 mg, 0.31 mmol) in dichloromethane (2 mL) 3 mmol/g triphenylphosphine supported on polymer (310 mg, 0.93 mmol), pyridin-4-ylmethanol (68 mg, 0.62 mmol) and 40% DEAD in toluene (270 mg, 0.62 mmol) at room temperature and the mixture was stirred at room temperature for 30 minutes. The mixture was purified by amino column chromatography (ethyl acetate-methanol) to obtain Compound II-105 (63 mg, 35%). [0296] LC/MS (ESI):m/z=575.00 [M+H]+, RT=1.43 min, method (2)

Reference： [1]Current Patent Assignee: SHIONOGI & CO., LTD. - JP5971830, 2016, B1 Location in patent: Paragraph 0082
[2]Current Patent Assignee: SHIONOGI & CO., LTD. - JP6267397, 2018, B1 Location in patent: Paragraph 0095
[3]Current Patent Assignee: SHIONOGI & CO., LTD. - US2020/261481, 2020, A1 Location in patent: Paragraph 0294-0296

49
[ 586-95-8 ]
[ 62-53-3 ]
[ 27768-46-3 ]

Yield	Reaction Conditions	Operation in experiment
93%	With Au/Zn0.02Al2O3; In toluene; at 60℃; under 760.051 Torr; for 10h;	General procedure: Oxidative coupling of alcohols and amines was performed in aWP-TEC-1020HC parallel reactor provided by WATTCASTM (WATTECSLAB EQUIPMENT CO., LTD.). In a typical protocol, 0.5 mmolbenzyl alcohol, 0.75 mmol aniline, 5 mL toluene and 40 mg catalystwere added successively. And then the reaction mixture was stirred (900 rpm) at 60 C under air (1 atm) for 8 h. The tube wasimmediately cooled in ice water and the reaction mixture wasanalysed using a Thermo Scientific TRACE 1310 gas chromatograph(GC) equipped with a flame ionization detector (FID) and a TR-5column (30 m 0.32 mm 0.25 lm). The quantification was carriedout using the external standard method. A series of toluenesolutions in different concentrations of benzyl alcohol, benzaldehydeor benzylideneaniline were used as external standard, respectively.Each reaction was at least repeated twice to guarantee areproducible result. The conversion of benzyl alcohol, the selectivityto alkylamines and the yield of imine were calculated, on thebasis of a carbon balance. For the reusability test, the catalystwas separated by centrifugation (8000 rpm for 10 min), washedthree times in turn with ethanol (100 mL) and water (100 mL),dried at 50 C for 24 h under vacuum, and was used for the nextrun.
79%	With oxygen; In toluene; at 80℃; for 24h;Schlenk technique;	Catalyst preparation As described in Example 1,The Schlenk flask was charged with 1 mmol4-pyridinemethanol and 1 mmol of aniline,0.125 g MnOx / HAP,2mL toluene as solvent,The air ball is an oxygen source,The reaction was stirred at 80 & lt; 0 & gt; C24h,To give the corresponding imine,The conversion was 99%The yield was 79%.

Reference： [1]Journal of Catalysis,2019,vol. 377,p. 110 - 121
[2]Patent: CN104710325,2016,B .Location in patent: Paragraph 0042; 0043
[3]Catalysis science and technology,2019,vol. 9,p. 286 - 301

50
[ 586-95-8 ]
cobalt(II) nitrate hexahydrate [ No CAS ]
[ 1934-75-4 ]
[Co(dicyanamide)₂(4-hydroxymethylpyridine)₂]_n [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
65%	In water at 80℃; for 2.5h;	2.2.1. Synthesis of [Co(dca)2(4-OMP)2]n (1) 0.29 g Co(NO3)2.6H2O (1 mmol), 0.18 g sodium dicyanamide(2 mmol) and 0.22 g 4-hydroxymethylpyridine (2 mmol) were dissolvedin 20 mL distilled H2O. The solution was heated up to 80 Cand stirred for 150 min. After filtration the clear pink solution wascooled down to RT. After 24 h pink plate-like crystals wereobtained (yield: 0.53 g, 65%). Anal. Calc. for C16H14N8O2Co(409.27 g/mol): 46.96% C; 3.45% H; 27.38% N. Found: 46.76% C;3.44% H; 27.37% N; IR (ATR, cm1): 3551(w), 3481 (w), 2269 (w),2245 (m), 2170 (s), 1606 (m), 1564 (w), 1504 (w), 1426 (m),1293 (s), 1202 (m), 1023 (vs), 799 (m), 607 (w), 533 (s), 493 (m).

Reference： [1]Mautner, Franz A.; Traber, Magdalena; Fischer, Roland C.; Massoud, Salah S.; Vicente, Ramon [Polyhedron, 2017, vol. 138, p. 13 - 20]

51
[ 586-95-8 ]
[ 17577-28-5 ]
[ 123293-78-7 ]
(Z)-ethyl 3-(pyridin-4-yl)acrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
72 % de	With [2,2]bipyridinyl; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; sodium hydroxide; copper(ll) bromide In formamide; acetonitrile at 65℃; for 24h; Schlenk technique; Overall yield = 69 %; Overall yield = 122 mg; diastereoselective reaction;	α,β-Unsaturated Esters 3, α,β-Unsaturated Ketones 4, and α,β-Unsaturated Nitriles 5; General Procedure General procedure: Alcohol (1 mmol), phosphonium salt (1.1 mmol), NaOH (1.1 mmol),CuBr2 (5 mol%), 2,2′-bipy (5 mol%), and TEMPO (5 mol%) were mixed in MeCN and HCONH2 (1:1, 2 mL) in a 100-mL Schlenk tube with an air balloon, and the mixture was stirred at 65 °C for 24 h (monitoring by TLC and/or GC-MS). After completion, product was purified by column chromatography (EtOAc and petroleum ether).

Reference： [1]Ding, Weijie; Hu, Juan; Jin, Huile; Yu, Xiaochun; Wang, Shun [Synthesis, 2018, vol. 50, # 1, p. 107 - 118]

52
[ 586-95-8 ]
[ 4441-56-9 ]
(2-cyclohexylpyridin-4-yl)methanol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
72%	Stage #1: pyridine-4-methanol With acetic acid; trifluoroacetic acid In acetonitrile at 20℃; for 0.166667h; Green chemistry; Stage #2: cyclohexylboronic acid With oxygen In acetonitrile at 110℃; for 12h; Green chemistry;

Reference： [1]Zhang, Lizhi; Liu, Zhong-Quan [Organic Letters, 2017, vol. 19, # 24, p. 6594 - 6597]

53
[ 586-95-8 ]
[ 75-15-0 ]
[ 1217190-74-3 ]

Yield	Reaction Conditions	Operation in experiment
93.1%		This compound was prepared following a reported procedure [15]. 4-Pyridylcarbinol (1.09g, 10mmol) was dissolved in dry THF (50mL) and added dropwise to a suspension of NaH (0.24g, 10mmol) in dry THF (100mL) under an inert atmosphere at -20C (a salt-ice bath). The mixture was stirred for 20min, then excess carbon disulfide (1.0mL, 1.6 excess) was added dropwise, and the resulting mixture was stirred for one hour while allowed to return to room temperature. The flask was disconnected from the Schlenk line, and the yellow solution was filtered to remove any solid impurities. The THF was removed under reduced pressure, and the resulting yellow powder was dried under vacuum; the solid (1.93g, yield 93.1%) was identified as 4-PyCH2OCS2Na; 1H NMR (acetone-d6): delta: 8.51 (d, J=5.9 Hz, 2H, Py), 7.35 (d, J=6.0 Hz, 2H, Py), 5.59 (s, 2H, Py-CH2)

Reference： [1]Inorganica Chimica Acta,2018,vol. 475,p. 161 - 171
[2]New Journal of Chemistry,2018,vol. 42,p. 18759 - 18764

54
[ 586-95-8 ]
[ 23806-24-8 ]
copper(II) nitrate [ No CAS ]
[Cu(3-methyl-2-thiophenecarboxylate)₂(4-pyridinemethanol)₂] [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With sodium hydroxide; In acetonitrile; for 3h;Reflux;	The blue crystals of II were prepared by dissolving of copper(II) nitrate (2.5 mmol) with double the quantities of <strong>[23806-24-8]3-methyl-2-thiophenecarboxylic acid</strong>, NaOH and 4-pyridinemethanol (5 mmol) in 50 cm3 of acetonitrile. The resulting solution was refluxed for 3 h and then left to slowly evaporate at ambient temperature. Well-shaped crystals were collected after a few days by filtration, washed with acetonitrile and finally dried at ambient temperature.

Reference： [1]Chemical Papers,2018,vol. 72,p. 863 - 876

55
[ 586-95-8 ]
[ 5994-87-6 ]
P,P-diphenyl-N-(pyridin-4-ylmethyl)phosphinic amide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	With carbonylhydrido(tetrahydroborato)[bis(2-diphenylphosphinoethyl)-amino]ruthenium(II); potassium hydroxide In toluene at 110℃; for 16h; Inert atmosphere; Sealed tube; Glovebox;	4.1. General Procedures General procedure: Glovebox Procedure (General Procedure 1): Inside an argonfilled glovebox (O2 levels between 35.0 and 55.0 ppm, H2O levels unknown), to an oven dried 10-mL screw cap vial equipped with a Teflon-coated magnetic stir bar were added Ru-MACHO (1.2 mg, 2.00 mmol), KOH (1.7 mg, 30.0 mmol), and the appropriate phosphinic amide (0.200 mmol) in that order. Subsequently, toluene (0.7 mL) was added via micropipette, with care taken to ensure that solids on the wall were washed to the bottom of the vial. Next, the appropriate alcohol (0.240 mmol) was added either as a solid or via micropipette for liquid substrates. The reaction was sealed tightly with a non-puncturable cap and was further sealed by placing a piece of electrical tape around the cap and top of vial. Schlenk Line Procedure (General Procedure 2): To a flame-dried vial were quickly added Ru-MACHO (1.2 mg, 2.00 mmol) and KOH (1.7 mg, 30.0 mmol) (stored under Ar) (addition time 1 min), and the reaction vial was left open under a steady flow of nitrogen (applied via a needle placed at the top of the vial). Next, the appropriate phosphinic amide (0.200 mmol) was added, followed by the addition of toluene (0.7 mL) from a standard Solvent Purification System (SPS). Lastly, the appropriate alcohol (0.240 mmol) was added either as a solid or via micropipette for liquid substrates. The nitrogen line was removed, and the vial was then quickly and tightly sealed with a non-puncturable cap and further sealed by placing a piece of electrical tape around the cap and top of the vial. After the differing series of operations described above, General Procedures 1 and 2 then followed then same protocol. The reaction vessel was placed in a preheated oil bath at 110e140 C with a stirring rate of 500 rpm. As the reaction was proceeding, the vessel was periodically visually monitored. If large amounts of solid were found to have accumulated on the wall, the vial was briefly removed from the oil bath and shaken to wash the solids back to the bottom of the vial. After 16 h, the vial was removed from the oil bath and allowed to cool to room temperature. Methanol (1 mL) was added to dissolve all solids, and the solvent removed in vacuo. The solid was redissolved in methanol (1 mL), and the solution was filtered through a 40-mm syringe filter. Samples were then purified by reverse-phase HPLC or recrystallized from hot benzene. In the case of HPLC purification, the fractions were combined, frozen in liquid N2, and lyophilized to sublime the solvent.

Reference： [1]Jankins, Tanner C.; Qin, Zi-Yang; Engle, Keary M. [Tetrahedron, 2019, vol. 75, # 24, p. 3272 - 3281]

56
[ 586-95-8 ]
[ 32249-35-7 ]
pyridin-4-ylmethyl 3-cyclopropyl-3-oxopropanoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
45%	With bismuth(III) chloride; In toluene; for 36h;Sealed tube; Molecular sieve; Reflux;	In a sealed flask, a mixture of 2.0 g of molecular sieves, 500 mg (4.58 mmol) of pyridin-4-ylmethanol, 0.83 mL (6.87 mmol) of <strong>[32249-35-7]methyl 3-cyclopropyl-3-oxopropanoate</strong> and 10% (0.45 mmol) of trichlorobismuthane in 10 mL of dry toluene was stirred at reflux for 36 hours. The reaction mixture was filtered and the filtrate concentrated, the remaining solid was purified by silica gel chromatography column (cyclohexane/ethyl acetate) to yield the desired β-keto ester (455 mg, 45%). 1H-NMR (400 MHz, DMSO-d6) δ = 0.94 (m, 4H), 2.12 (ddd, 1H), 3.86 (s, 2H), 5.20 (s, 2H), 7.36 (d, 2H), 8.56 (d, 2H). HPLC-MS: Rt 3.040; m/z 220.1 (MH+).

Reference： [1]Patent: EP3480201,2019,A1 .Location in patent: Paragraph 0270; 0271

57
[ 586-95-8 ]
[ 21101-56-4 ]
1,2-bis(3-(pyridin-4-ylmethoxy)phenyl)disulfane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
46.3%	With di-isopropyl azodicarboxylate; triphenylphosphine In tetrahydrofuran at 0 - 20℃; for 15h; Inert atmosphere;
	With di-isopropyl azodicarboxylate; triphenylphosphine In tetrahydrofuran at 0 - 20℃; for 15h; Inert atmosphere;

Reference： [1]Current Patent Assignee: NAT INSTITUTE OF BIOLOGICAL SCIENCES BEIJING; NATIONAL INSTITUTE OF BIOLOGICAL SCIENCES - WO2019/196953, 2019, A1 Location in patent: Paragraph 0276
[2]Liu, Yang; Ruan, Hanying; Li, Ying; Sun, Guoliang; Liu, Xiao; He, Wenhui; Mao, Fengfeng; He, Miaomiao; Yan, Liwei; Zhong, Guocai; Yan, Huan; Li, Wenhui; Zhang, Zhiyuan [Journal of Medicinal Chemistry, 2021, vol. 64, # 1, p. 543 - 565]

58
[ 586-95-8 ]
[ 21101-56-4 ]
3-(pyridin-4-ylmethoxy)benzenethiol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: di-isopropyl azodicarboxylate; triphenylphosphine / tetrahydrofuran / 15 h / 0 - 20 °C / Inert atmosphere 2: tributylphosphine / tetrahydrofuran / 3 h / 20 °C
	Multi-step reaction with 2 steps 1: triphenylphosphine; di-isopropyl azodicarboxylate / tetrahydrofuran / 15 h / 0 - 20 °C / Inert atmosphere 2: tributylphosphine / tetrahydrofuran / 3 h / 20 °C / Inert atmosphere

Reference： [1]Current Patent Assignee: NAT INSTITUTE OF BIOLOGICAL SCIENCES BEIJING; NATIONAL INSTITUTE OF BIOLOGICAL SCIENCES - WO2019/196953, 2019, A1
[2]Liu, Yang; Ruan, Hanying; Li, Ying; Sun, Guoliang; Liu, Xiao; He, Wenhui; Mao, Fengfeng; He, Miaomiao; Yan, Liwei; Zhong, Guocai; Yan, Huan; Li, Wenhui; Zhang, Zhiyuan [Journal of Medicinal Chemistry, 2021, vol. 64, # 1, p. 543 - 565]

59
[ 586-95-8 ]
[ 155-12-4 ]
C₁₀H₈FN₃O₂ [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2019,vol. 141,p. 16288 - 16295

60
[ 586-95-8 ]
[ 923169-37-3 ]

Reference： [1]Patent: US2019/352288,2019,A1

61
[ 586-95-8 ]
[ 2244190-24-5 ]
[ 811803-05-1 ]

Yield	Reaction Conditions	Operation in experiment
16.7 mg	With potassium hydroxide In N,N-dimethyl-formamide at 150℃; for 36h; Inert atmosphere; Sealed tube;	10 Example 10: Synthesis of drug molecule Apatinib (Apatinib, compound 57c-1) In a 10 mL dry sealed reaction tube, sequentially add 1,2,3-triazine 2a (8.1 mg, 0.10 mmol), N- (4- (1-cyanocyclopentyl) phenyl) -2-cyanoacetamide 8b (27.8 mg, 0.11 mmol) and potassium hydroxide (8.4 mg, 0.15 mmol). After nitrogen substitution three times, the solvent N, N-dimethylformamide (1.5 mL) was added, and the sealed reaction tube was placed at 100 ° C. for 8 h. The reaction was monitored by TLC. After the reaction was complete, potassium hydroxide (11.2 mg, 0.20 mmol) and 4-pyridinemethanol (16.4 mg, 0.15 mmol) were added, and the sealed reaction tube was placed at 150 ° C for 36 h. The reaction was monitored by TLC. After the reaction was completed, it was extracted with dichloromethane (3 * 10 mL). The organic phase was dried over anhydrous sodium sulfate and concentrated in vacuo. After column chromatography, the target product was obtained as a white solid 56c-2 (16.7 mg, 42 %).

Reference： [1]Current Patent Assignee: CHONGQING UNIVERSITY - CN111004284, 2020, A Location in patent: Paragraph 0086-0088

62
[ 586-95-8 ]
[ 89-56-5 ]
[ 142-71-2 ]
[Cu(5-methylsalicylate)₂(µ-4-pyridylmethanol)₂]_n [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
63.16%	In ethanol; water	Complex 4 [Cu(5-MeSal)₂(µ-4-PM)₂]_n Blue crystals were obtained from water-ethanol or water-acetonitrile mixture solvent in ratio 1:1 or 1:3. 4-pyridylmethanol (2mmol, 0.218g) was added to a water solution of copper acetate (0.5mmol, 0.1M). The appropriate amount of acid (1mmol) was added to reaction mixture under stirring. The blue-green precipitates were separated after few hours stirring and the mother liquids were left forcrystallization. The crystals were separated after few weeks at laboratory temperature. (0023) [Cu(5-MeSal)2(µ-4-PM)2]n, Yield: 63.16%, 0.185g (0024) Anal Calc: C, 57.78; H, 4.83; N, 4,80. Found: C, 57.42; H, 4.52; N, 4.74. (0025) IR (ATR/cm-1): 3124(w), 1630(m), 1618(s), 1605(m), 1566(s), 1548(m), 1422(s), 1060(ms), 769 (s). (0026) UV-Vis (λ/nm):614.

Reference： [1]Puchoňová, Miroslava; Maroszová, Jaroslava; Vasková, Zuzana; Mazúr, Milan; Valigura, Dušan; Koman, Marian; Moncol, Jan [Inorganica Chimica Acta, 2020, vol. 510]

63
[ 586-95-8 ]
[ 13938-94-8 ]
silver nitrate [ No CAS ]
[Rh(PPh₃)₂(CO)(4-pyridinemethanol)][NO₃] [ No CAS ]

Reference： [1]Dalton Transactions,2020,vol. 49,p. 13029 - 13043

64
[ 586-95-8 ]
[ 2466-76-4 ]
[ 217192-22-8 ]
[ 1007-48-3 ]
C₁₄H₁₃NO₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
1: 14 %Spectr. 2: 11 %Spectr.	With C₃₀H₂₈CuN₂⁽²⁺⁾ In dichloromethane-d2; [D₃]acetonitrile at 50℃; for 24h;

Reference： [1]Goswami, Abir; Gaikwad, Sudhakar; Schmittel, Michael [Chemistry - A European Journal, 2021, vol. 27, # 9, p. 2997 - 3001]

65
[ 586-95-8 ]
[ 152121-41-0 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1.1: 1H-imidazole / N,N-dimethyl-formamide / 20 °C 2.1: n-butyllithium; N,N-diisopropylamine / tetrahydrofuran; hexanes / -78 - 20 °C 2.2: 20 °C 2.3: 1 h / 20 °C 3.1: oxalyl dichloride; dimethyl sulfoxide / dichloromethane / 0.5 h / -60 °C 3.2: -60 - 20 °C

Reference： [1]Current Patent Assignee: ALMIRALL SA - WO2007/17096, 2007, A1

66
[ 586-95-8 ]
[ 1895006-01-5 ]
[ 1099598-10-3 ]

Yield	Reaction Conditions	Operation in experiment
45%	Stage #1: pyridin-4-ylmethanol With pyridine; 5,7-di-tert-butyl-3-phenylbenzo[d]oxazol-3-ium tetrafluoroborate In 2-methoxy-2-methylpropane at 20℃; for 1h; Inert atmosphere; Stage #2: Umemoto’s reagent With Quinuclidine; C₃₆H₂₂F₁₀IrN₄O₂⁽¹⁺⁾*F₆P^(1-); tetra-n-butyl-ammonium chloride; copper chloride (II) In dimethyl sulfoxide at 20℃; for 8h; Irradiation; Inert atmosphere; Sealed tube;

Reference： [1]Intermaggio, Nicholas E.; Millet, Agustin; Davis, Dali L.; MacMillan, David W. C. [Journal of the American Chemical Society, 2022, vol. 144, # 27, p. 11961 - 11968]

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[ CAS No. 586-95-8 ] {[proInfo.proName]}

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