Name: 4039-82-1|((Prop-2-yn-1-yloxy)methyl)benzene|97%
Brand: Ambeed
SKU: A729215
Price: 5.0 USD
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1
[ 100-44-7 ]
[ 107-19-7 ]
[ 4039-82-1 ]

Yield	Reaction Conditions	Operation in experiment
80%	With tert-butylammonium hydrogen sulphate; sodium hydroxide for 3h; Ambient temperature;
73%	Stage #1: propargyl alcohol With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; for 1h; Stage #2: benzyl chloride In N,N-dimethyl-formamide; mineral oil at 0 - 20℃; for 18h;	General Procedure for Synthesis of Propargyl Ethers (C) General procedure: The alcohol derivative (1 eq) was dissolved in anhydrous DMF and cooled to 0 °C. NaH (60% dispersion in mineral oil, 2 eq) was added portion-wise and the reaction mixture was stirred for 1 h. Propargyl bromide (1.5 eq) was added dropwise and the solution was allowed to warm to r.t. and stirred for a further 18 h. The reaction was quenched by the addition of H2O before being extracted with EtOAc. The combined organic layers were then washed sequentially with saturated NaHCO3 (aq) solution, H2O and Brine. The organic layer was dried over MgSO4, filtered and concentrated under reduced pressure. The crude material was then purified by flash column chromatography.
47%	Stage #1: propargyl alcohol With sodium hydride In tetrahydrofuran; mineral oil at 0℃; for 0.25h; Stage #2: benzyl chloride With tetra-(n-butyl)ammonium iodide In tetrahydrofuran; mineral oil at 0 - 24℃; for 16h;

	With potassium hydroxide
	With sodium hydroxide In benzene
	With potassium hydroxide; cetyltributylphosphonium bromide 1.) C₆H₆, room temp., 15 min, 2.) 70 deg C, 3 h; Yield given. Multistep reaction;
	With sodium hydride In tetrahydrofuran at 80℃; for 8h;
	Stage #1: propargyl alcohol With sodium hydride In tetrahydrofuran at 0℃; for 1h; Stage #2: benzyl chloride In tetrahydrofuran at 20℃;

Reference： [1]Baskaran, Subramanian; Baskaran, Chitra; Trivedi, Girish K. [Journal of Chemical Research, Miniprint, 1997, # 11, p. 2459 - 2471]
[2]Alderwick, Luke J.; Armstrong, Tom; Lamont, Malcolm; Lanne, Alice; Thomas, Neil R. [Bioorganic and Medicinal Chemistry, 2020, vol. 28, # 22]
[3]Xiao, Zu-Feng; Ding, Ting-Hui; Mao, Sheng-Wei; Ning, Xiao-Shan; Kang, Yan-Biao [Advanced Synthesis and Catalysis, 2016, vol. 358, # 11, p. 1859 - 1863]
[4]Marszak et al. [Memorial des services chimiques de l'Etat, 1950, vol. 35, p. 67,71]
[5]Shikhiev,I.A. et al. [Journal of Organic Chemistry USSR (English Translation), 1975, vol. 11, p. 2168 - 2170][Zhurnal Organicheskoi Khimii, 1975, vol. 11, # 10, p. 2134 - 2137]
[6]Manzocchi, Ada; Fiecchi, Alberto; Santaniello, Enzo [Synthesis, 1987, # 11, p. 1007 - 1009]
[7]Montevecchi, Pier Carlo; Navacchia, Maria Luisa [Journal of Organic Chemistry, 1998, vol. 63, # 3, p. 537 - 542]
[8]Wang, Cheng-Qiang; Ye, Lu; Feng, Chao; Loh, Teck-Peng [Journal of the American Chemical Society, 2017, vol. 139, # 5, p. 1762 - 1765]

2
[ 106-96-7 ]
[ 100-51-6 ]
[ 4039-82-1 ]

Yield	Reaction Conditions	Operation in experiment
96%	With potassium hydroxide In dimethyl sulfoxide at 23℃; for 1h;
95%	Stage #1: benzyl alcohol With sodium hydride In tetrahydrofuran at -20 - 20℃; Inert atmosphere; Stage #2: propargyl bromide In tetrahydrofuran at 0 - 20℃; Inert atmosphere;
93%	Stage #1: benzyl alcohol With potassium hydride In tetrahydrofuran at 0℃; for 0.5h; Stage #2: propargyl bromide In toluene at 20℃; for 1h; Further stages.;

91%	With sodium hydride In N,N-dimethyl-formamide at 0 - 20℃;
87%	With potassium hydroxide In dimethyl sulfoxide at 0 - 20℃; for 1h;
80%	Stage #1: benzyl alcohol With sodium hydride In tetrahydrofuran; mineral oil at 0℃; Stage #2: propargyl bromide In tetrahydrofuran; toluene; mineral oil at 0 - 20℃; for 24h; Inert atmosphere;
76%	With sodium hydride In N,N-dimethyl-formamide
71%	With potassium hydroxide In dimethyl sulfoxide at 0 - 20℃;
70%	Stage #1: benzyl alcohol With sodium hydride In tetrahydrofuran at 0 - 20℃; for 0.5h; Stage #2: propargyl bromide In tetrahydrofuran; toluene at 0 - 20℃; for 6h;
60%	With cesium fluoride In acetonitrile
60%	With cesium fluoride In acetonitrile
59%	Stage #1: benzyl alcohol With sodium hydride In tetrahydrofuran at 0℃; for 0.5h; Stage #2: propargyl bromide In tetrahydrofuran
59%	Stage #1: benzyl alcohol With sodium hydride In tetrahydrofuran at 0℃; for 0.5h; Stage #2: propargyl bromide In tetrahydrofuran; toluene
51.7%	Stage #1: benzyl alcohol With sodium hydride In tetrahydrofuran at -20 - 20℃; for 0.333333h; Stage #2: propargyl bromide In tetrahydrofuran at 0 - 20℃; for 24h; Inert atmosphere;	68.1 Step 1: Synthesis of compound ((prop-2-yn-1-yloxy) methyl) benzene Benzyl alcohol (700 mg, 6.47 mmol) was dissolved in THF (35 mL), sodium hydride (360 mg, 7.77 mmol) was slowly added at -20 ° C, and the temperature was raised to room temperature and stirred for 20 min.3-Bromopropyne (1.0g, 7.77mmol) was slowly added at 0 ° C, protected by nitrogen, and reacted at room temperature for 24 hours.The stirring was stopped, the celite was filtered, and the solvent was concentrated. Water (60 mL) was added and extracted with ethyl acetate (50 mL × 3).The organic phase was collected, dried over anhydrous sodium sulfate, filtered and concentrated.Silica gel column chromatography was separated and purified (PE / EtOAc (v / v) = 60/1) to obtain 490 mg of light yellow liquid, yield: 51.7%.
	(i) NaH, 1,2-dimethoxy-ethane, (ii) /BRN= 605309/; Multistep reaction;
	With potassium hydroxide In dimethyl sulfoxide at 20℃;
	Stage #1: benzyl alcohol With potassium hydroxide In dimethyl sulfoxide for 0.166667h; Stage #2: propargyl bromide In dimethyl sulfoxide at 0 - 20℃; for 3h;	4.2.2. Synthesis of methyl (4-((prop-2-ynyloxy) methyl) phenyl) sulfane (3) General procedure: To a suspension of KOH (16.8 g, 0.30 mol) in 100 mL DMSO was added 4-methylthiobenzyl alcohol (15.4 g, 0.10 mol). After stirring for 10 min, propargyl bromide (8.8 mL, 0.10 mol) was added at 0 °C. Stirring was continued for 3 h at room temperature. The resulting suspension was diluted with 200 mL water and was extracted with diethyl ether (3 × 100 mL). The combined organic layers were washed with water (4 × 60 mL), brine, dried over Na2SO4, filtered and concentrated under reduced pressure. The obtained yellowish residue was purified by silica gel column chromatography eluting with diethyl ether/hexane (2:8) to afford the title compound 3 as a colorless liquid (17.10 g, 89.0% yield).
	Stage #1: benzyl alcohol With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; for 2h; Stage #2: propargyl bromide In N,N-dimethyl-formamide; mineral oil at 0 - 20℃;	4.2. General procedure for the synthesis of alkynes 1k-r30 General procedure: To a stirred solution of alcohol (14.5 mmol, 1.0 equiv) in anhydrous DMF (25 mL) was added sodium hydride (60 percent in oil,1.16 g, 29 mmol, 2.0 equiv) at 0°C. The mixture was further stirredat 0°C for 2 h before slowly addition of propargyl bromide (2.59 g,21.6 mmol, 1.5 equiv). After stirred at room temperature overnight,the reaction was quenched by addition of ice-water and extracted with EtOAc twice. The combined organic phase was washed with brine and dried over MgSO4. Evaporation of solvent provided the crude product as a color residue. The crude product was purified by column chromatography on silica gel with mixture of petroleum ether and ethyl acetate to afford alkynes 1k-r.
	Stage #1: benzyl alcohol With sodium hydride In N,N-dimethyl-formamide at 0℃; for 0.333333h; Inert atmosphere; Stage #2: propargyl bromide In N,N-dimethyl-formamide at 20℃; for 1h; Inert atmosphere;
	Alkaline conditions;
	With sodium hydride In tetrahydrofuran at 0 - 20℃; for 2h;

Reference： [1]Boger, Dale L.; Palanki, Moorthy S.S. [Journal of the American Chemical Society, 1992, vol. 114, # 24, p. 9318 - 9327]
[2]Li, Hui-Jing; Guillot, Regis; Gandon, Vincent [Journal of Organic Chemistry, 2010, vol. 75, # 24, p. 8435 - 8449]
[3]Sammelson, Robert E.; Miller, R. Bryan; Kurth, Mark J. [Journal of Organic Chemistry, 2000, vol. 65, # 7, p. 2225 - 2228]
[4]Guanti, Giuseppe; Perrozzi, Sara; Riva, Renata [Tetrahedron Asymmetry, 2002, vol. 13, # 24, p. 2703 - 2706]
[5]Martinez, Claudio; Wu, Yichen; Weinstein, Adam B.; Stahl, Shannon S.; Liu, Guosheng; Muniz, Kilian [Journal of Organic Chemistry, 2013, vol. 78, # 12, p. 6309 - 6315]
[6]Elbert, Bryony L.; Lim, Diane S. W.; Gudmundsson, Haraldur G.; O'Hanlon, Jack A.; Anderson, Edward A. [Chemistry - A European Journal, 2014, vol. 20, # 28, p. 8594 - 8598]
[7]Mendoza-Espinosa, Daniel; Negron-Silva, Guillermo; Lomas-Romero, Leticia; Gutierrez-Carrillo, Atilano; Santillan, Rosa [Synthetic Communications, 2014, vol. 44, # 6, p. 807 - 817]
[8]Location in patent: experimental part Shore, Gjergji; Organ, Michael G. [Chemistry - A European Journal, 2008, vol. 14, # 31, p. 9641 - 9646]
[9]Ji, Kegong; Zhang, Liming [Advanced Synthesis and Catalysis, 2018, vol. 360, # 4, p. 647 - 651]
[10]Shah, Syed Tasadaque A; Khan, Khalid M; Heinrich, Angelica M; Choudhary, M.Iqbal; Voelter [Tetrahedron Letters, 2002, vol. 43, # 47, p. 8603 - 8606]
[11]Shah, Syed Tasadaque Ali; Khan, Khalid Mohammed; Hussain, Hidayat; Anwar, Muhammad Usman; Fecker, Miriam; Voelter, Wolfgang [Tetrahedron, 2005, vol. 61, # 27, p. 6652 - 6656]
[12]Xu, Zhou; Chen, Hongyi; Wang, Zhixun; Ying, Anguo; Zhang, Liming [Journal of the American Chemical Society, 2016, vol. 138, # 17, p. 5515 - 5518]
[13]Zhai, Rong L.; Xue, Yun S.; Liang, Ting; Mi, Jia J.; Xu, Zhou [Journal of Organic Chemistry, 2018, vol. 83, # 17, p. 10051 - 10059]
[14]Current Patent Assignee: SHENZHEN DONGYANGGUANG INDUSTRIAL DEVELOPMENT CO LTD - CN107344940, 2020, B Location in patent: Paragraph 1201-1205
[15]Kwart,H. et al. [Journal of the American Chemical Society, 1973, vol. 95, p. 5234 - 5242]
[16]Location in patent: experimental part Kuang, Jinqiang; Shengming, Ma. [Journal of Organic Chemistry, 2009, vol. 74, # 4, p. 1763 - 1765]
[17]Location in patent: experimental part Reddy, Nimmanapalli P.; Chandramohan Reddy; Aparoy, Polamarasetty; Achari, Chandrani; Sridhar, P. Ramu; Reddanna, Pallu [European Journal of Medicinal Chemistry, 2012, vol. 47, # 1, p. 351 - 359]
[18]Fan, Xiaohui; Li, Na; Shen, Tong; Cui, Xiao-Meng; Lv, Hao; Zhu, Hong-Bo; Guan, Yong-Hong [Tetrahedron, 2014, vol. 70, # 2, p. 256 - 261]
[19]Huple, Deepak B.; Mokar, Bhanudas D.; Liu, Rai-Shung [Angewandte Chemie - International Edition, 2015, vol. 54, # 49, p. 14924 - 14928][Angew. Chem., 2016, vol. 127, # 49, p. 15137 - 15141,5]
[20]Negi, Beena; Kumar, Deepak; Kumbukgolla, Widuranga; Jayaweera, Sampath; Ponnan, Prija; Singh, Ramandeep; Agarwal, Sakshi; Rawat, Diwan S. [European Journal of Medicinal Chemistry, 2016, vol. 115, p. e426 - e437]
[21]Wang, Jun; Yang, Zhiping [Angewandte Chemie - International Edition, 2021, vol. 60, # 52, p. 27288 - 27292][Angew. Chem., 2021, vol. 133, # 52, p. 27494 - 27498]

3
[ 4039-82-1 ]
[ 22539-93-1 ]

Yield	Reaction Conditions	Operation in experiment
55%		General procedure: To a suspension of Au(DPB)Cl (4.0×10-3 mmol) in 1,2-dichloroethane was added AgSbF6 (4.0×10-3mmol) at room temperature. After stirring for 30 min, to a solution of Au(DPB)SbF6 in1,2-dichloroethane and MeOH (0.50 mmol) was added alkyne 4 at room temperature. The solventwas evaporated off. The residue was chromatographed with hexane-AcOEt to afford hydratedproduct. The results are shown in Table 2.

Reference： [1]Journal of the American Chemical Society,1992,vol. 114,p. 9318 - 9327
[2]Synthesis,1987,p. 1007 - 1009
[3]Organic Letters,2012,vol. 14,p. 1548 - 1551
[4]Journal of Organic Chemistry,2002,vol. 67,p. 7613 - 7617
[5]Chemistry Letters,2018,vol. 47,p. 1321 - 1323
[6]Journal of Organic Chemistry USSR (English Translation),1975,vol. 11,p. 2168 - 2170
Zhurnal Organicheskoi Khimii,1975,vol. 11,p. 2134 - 2137

4
[ 4039-82-1 ]
[ 541-41-3 ]
[ 138435-42-4 ]

Yield	Reaction Conditions	Operation in experiment
91%	With n-butyllithium In tetrahydrofuran; hexane 1.) -78 deg C, 10 min, 2.) -78 deg C to 0 deg C;
88%	With n-butyllithium
84%	Stage #1: Benzyl propargyl ether With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1.41667h; Stage #2: chloroformic acid ethyl ester In tetrahydrofuran; hexane at -78 - 0℃; for 1.03333h; Further stages.;

83%	Stage #1: Benzyl propargyl ether With methyllithium In tetrahydrofuran; diethyl ether at -78℃; for 0.5h; Stage #2: chloroformic acid ethyl ester In tetrahydrofuran; diethyl ether at -78 - 20℃;
72%	Stage #1: Benzyl propargyl ether With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Stage #2: chloroformic acid ethyl ester In tetrahydrofuran; hexane at -78 - 20℃; Further stages.;
	With n-butyllithium 1.) THF, hexane, -70 to 5 deg C, 2 h, 2.) -70 to 5 deg C, 110 min; Yield given. Multistep reaction;
	With n-butyllithium 1) THF, hexane, -78 deg C, 10 min; 2) THF, hexane; Yield given. Multistep reaction;
	Stage #1: Benzyl propargyl ether With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Inert atmosphere; Stage #2: chloroformic acid ethyl ester In tetrahydrofuran; hexane at -78 - 20℃; Inert atmosphere;

Reference： [1]Cook, Gregory R.; Beholz, Lars G.; Stille, John R. [Journal of Organic Chemistry, 1994, vol. 59, # 13, p. 3575 - 3584]
[2]Cook, Gregory R.; Beholz, Lars G.; Stille, John R. [Tetrahedron Letters, 1994, vol. 35, # 11, p. 1669 - 1672]
[3]Armstrong, Alan; Barsanti, Paul A.; Jones, Lyn H.; Ahmed, Ghafoor [Journal of Organic Chemistry, 2000, vol. 65, # 21, p. 7020 - 7032]
[4]Narczyk, Aleksandra; Stecko, Sebastian [Organic and Biomolecular Chemistry, 2020, vol. 18, # 6, p. 1204 - 1213]
[5]Fischer, Daniel F.; Xin, Zhuo-Qun; Peters, Rene [Angewandte Chemie - International Edition, 2007, vol. 46, # 40, p. 7704 - 7707]
[6]Heathcock, Clayton H.; Stafford, Jeffrey A.; Clark, David L. [Journal of Organic Chemistry, 1992, vol. 57, # 9, p. 2575 - 2585]
[7]Beholz, Lars G.; Benovsky, Petr; Ward, Donald L.; Barta, Nancy S.; Stille, John R. [Journal of Organic Chemistry, 1997, vol. 62, # 4, p. 1033 - 1042]
[8]Fischer, Daniel F.; Barakat, Assem; Xin, Zhuo-Qun; Weiss, Matthias E.; Peters, Rene [Chemistry - A European Journal, 2009, vol. 15, # 35, p. 8722 - 8741]

5
[ 100-39-0 ]
[ 107-19-7 ]
[ 4039-82-1 ]

Yield	Reaction Conditions	Operation in experiment
100%	Stage #1: Prop-2-ynyl alcohol With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; Stage #2: benzyl bromide In N,N-dimethyl-formamide; mineral oil at 20℃;
98%	With N,N,N-tributyl-1-butanaminium iodide; sodium hydride In N,N-dimethyl-formamide at 0 - 20℃;
98%	With tetrabutylammonium bromide; sodium hydroxide In water monomer; toluene at 50℃; for 15h;

98%	With sodium hydride In tetrahydrofuran at 0 - 20℃; for 6h;
98%	Stage #1: Prop-2-ynyl alcohol With sodium hydride In tetrahydrofuran; mineral oil at 0℃; for 0.5h; Stage #2: benzyl bromide In tetrahydrofuran; mineral oil at 0 - 20℃; for 2h;
94%	With sodium hydroxide In dimethyl sulfoxide at 20℃; for 24h;
93%	With N,N,N-tributyl-1-butanaminium iodide; sodium hydride In tetrahydrofuran for 7.5h; Ambient temperature;
93.4%	With sodium hydroxide; tetrabutylammonium bromide In water monomer; toluene at 50℃; for 4h;	I1.A Tetrabutylammonium bromide (19.34 g, 600 mmol) was added to a solution of benzylbromide (71.3 ml, 600 mmol) and propargyl alcohol (35.5 ml, 600 mmol) in 270 ml of toluene and the mixture was heated to 50°C. A solution of sodium hydroxide (24 g, 600 mmol) in 55 ml of water was then added dropwise over a period of 1 hour and stirring was continued for another 3 hours. The reaction mixture was then cooled to 25°C and transferred into a separatory funnel. The aqueous layer was removed and the organic layer was washed three times with 150 ml of brine. Residual water was removed by repeated azeotropic distillation using toluene. A pale yellow liquid was obtained. Yield: 81. 9 g (93. 4 %). MS (El) : 145 [M-H]- 'H NMR (CDC13), 8 (ppm): 7.29-7. 40 (m, 5H), 4.64 (s, 2H), 4.20 (d, 2H), 2.49 (t, 1H).
92%	Stage #1: Prop-2-ynyl alcohol With sodium hydride In tetrahydrofuran at 0 - 20℃; for 1h; Stage #2: benzyl bromide With N,N,N-tributyl-1-butanaminium iodide In tetrahydrofuran
92%	Stage #1: Prop-2-ynyl alcohol With sodium hydride In tetrahydrofuran at 0 - 20℃; for 0.1h; Inert atmosphere; Schlenk technique; Stage #2: benzyl bromide With N,N,N-tributyl-1-butanaminium iodide In tetrahydrofuran at 20℃; for 12h; Inert atmosphere; Schlenk technique;	((Prop-2-yn-1-yloxy)methyl)benzene (2k) (CAS 4039-82-1) To a stirred suspension of sodium hydride (240 mg, 10 mmol, 1 equiv) in THF (20 mL) maintained at 0 oCpropargyl alcohol (0.6 mL, 10 mmol, 1 equiv) in THF (5 mL) was added. The resulting mixture was warmed toroom temperature (c.a.1 h). Then, tetrabutylammonium iodide (185 mg, 0.5 mmol, 0.05 equiv) and benzylbromide (1.3 mL, 11 mmol, 1.1equiv) in THF (5 mL) were added successively. The reaction mixture was stirredat the same temperature for additional 12 h monitored by TLC (SiO2, petroleum ether/ethyl acetate 20:1). Aftercompleted, the reaction was diluted with Et2O (30 mL) and quenched with water (5 mL). The layers wereseparated and the aqueous layer was extracted with Et2O (3 × 50 mL). The combined organic layers were washedwith brine (50 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The residuewas purified by silica gel chromatography (petroleum ether/ethyl acetate 20:1) to afford 2k as a yellow oil (1.35g, 92% yield). 1H NMR (300 MHz, CDCl3) δ 7.37 - 7.32 (m, 5H), 4.62 (s, 2H), 4.18 (d, J = 2.4 Hz, 2H), 2.47 (t,J = 2.4 Hz, 1H); 13C NMR (75 MHz, CDCl3) δ 137.2, 128.3, 128.0, 127.8, 79.6, 74.5, 71.4, 57.0. Thecharacterization data for this compound match the literature data.
91%	With N,N,N-tributyl-1-butanaminium iodide; sodium hydride In N,N-dimethyl-formamide at 0 - 20℃; for 24h;
88%	Stage #1: Prop-2-ynyl alcohol With potassium hydroxide In dimethyl sulfoxide at 0℃; for 0.166667h; Stage #2: benzyl bromide In dimethyl sulfoxide at 20℃; for 3h;
86%	Stage #1: Prop-2-ynyl alcohol With potassium hydroxide In dimethyl sulfoxide at 0 - 20℃; Stage #2: benzyl bromide In dimethyl sulfoxide at 0 - 20℃;
86%	Stage #1: Prop-2-ynyl alcohol With sodium hydride; sodium iodide In N,N-dimethyl-formamide at 0℃; Inert atmosphere; Stage #2: benzyl bromide In N,N-dimethyl-formamide at 0 - 20℃; Inert atmosphere;
86%	Stage #1: Prop-2-ynyl alcohol With N,N,N-tributyl-1-butanaminium iodide; sodium hydride In tetrahydrofuran at 0℃; for 0.333333h; Inert atmosphere; Stage #2: benzyl bromide In tetrahydrofuran at 0 - 20℃; Inert atmosphere;
86%	Stage #1: Prop-2-ynyl alcohol With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; for 1h; Stage #2: benzyl bromide In N,N-dimethyl-formamide at 0 - 20℃;
84%	With sodium hydride In N,N-dimethyl-formamide; mineral oil at 22℃; for 22h;
83%	With sodium hydride In tetrahydrofuran
81%	With sodium hydride In tetrahydrofuran; N,N-dimethyl-formamide at 0 - 20℃; for 17h;
80%	With sodium hydride In tetrahydrofuran 1.) overnight, 2.) 4 h;
79%	With tetra-n-butyl-ammonium chloride In hexane at 20℃; for 6h;
77%	With natrium In toluene Heating;
77%	Stage #1: Prop-2-ynyl alcohol With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; for 0.5h; Stage #2: benzyl bromide In N,N-dimethyl-formamide; mineral oil at 20℃; for 14h;	1.2.2 Synthesis of ((prop-2-yn-1-yloxy)methyl)benzene (1b) To a suspension of NaH (60 % in mineral oil, 2.27 g, 56.67 mmol, 1.1 eq.) in 50 ml of DMFwere added dropwise via syringe 3.0 ml (51.54 mmol, 1.0 eq.) of propargylic alcohol at 0 °C.After 30 min, 6.74 ml (56.67 mmol, 1.1 eq.) of benzyl bromide were added and the reactionmixture was stirred at r.t. for 14 h. Then, the mixture was diluted with 100 ml of EtOAc,washed with 100 ml of HCl (1 mol/l), the organic layer was dried over MgSO4 and the solventwas removed under reduced pressure. The crude product was purified by flash columnchromatography (cHex/CH2Cl2 100:0 - 0:100). The product was obtained as a slightly yellowoil (yield: 5.77 g, 39.4 mmol, 77 %).
77%	With potassium hydroxide In dimethyl sulfoxide at 0 - 27℃; for 3h;
75%	Stage #1: Prop-2-ynyl alcohol With sodium hydride In N,N-dimethyl-formamide at 20℃; for 0.5h; Stage #2: benzyl bromide In N,N-dimethyl-formamide at 20℃; for 0.5h; Further stages.;
75%	Stage #1: Prop-2-ynyl alcohol With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0 - 20℃; Inert atmosphere; Stage #2: benzyl bromide In N,N-dimethyl-formamide; mineral oil at 0 - 20℃; Inert atmosphere;
71%	With potassium carbonate In N,N-dimethyl-formamide at 20℃;
69%	Stage #1: Prop-2-ynyl alcohol With sodium hydride In N,N-dimethyl-formamide; mineral oil at 20℃; for 0.5h; Stage #2: benzyl bromide In N,N-dimethyl-formamide; mineral oil at 20℃;
66%	In tetrahydrofuran
61%	Stage #1: Prop-2-ynyl alcohol With sodium hydride In tetrahydrofuran at 0℃; for 1h; Inert atmosphere; Stage #2: benzyl bromide With N,N,N-tributyl-1-butanaminium iodide In tetrahydrofuran at 20℃; for 18h; Inert atmosphere;
59%	Stage #1: Prop-2-ynyl alcohol With potassium hydroxide In dimethyl sulfoxide at 0℃; for 0.166667h; Stage #2: benzyl bromide In dimethyl sulfoxide at 0 - 20℃;
53.1%	Stage #1: Prop-2-ynyl alcohol With sodium hydride In N,N-dimethyl-formamide at 0℃; for 1h; Inert atmosphere; Stage #2: benzyl bromide In N,N-dimethyl-formamide at 0 - 20℃; for 16h; Inert atmosphere;	5.1 Step 1: ((Prop-2-ynyloxy)methyl)benzene (S2) [0474] To a solution of Scheme 5-7 compound SI (15.5 g, 0.277 mol) in dry DMF (150 mL) was added NaH (12 g, 305 mol) at 0 °C slowly. After stirring at 0 °C for 1 h, BnBr (52 g, 305 mol) was added into the above mixture at 0 °C. The reaction was stirred at room temperature for 16 h. The mixture was quenched with saturated aq. NELCl solution (150 mL) and then extracted with DCM (300 mL). The organic layer was washed with aq. LiCl solution (150 mL x 3), dried over anhydrous Na2S04 and concentrated. The residue was purified by column chromatography on silica gel (eluted with petroleum ether: ethyl acetate =100:0 to 100: 1) to afford the title compound (21 g, 53.1 % yield) as a colorless oil.
53.1%	Stage #1: Prop-2-ynyl alcohol With sodium hydride In N,N-dimethyl-formamide at 0℃; for 1h; Stage #2: benzyl bromide In N,N-dimethyl-formamide at 0 - 20℃; for 16h;	5.1 Step 1: ((Prop-2-ynyloxy)methyl)benzene (S2) To a solution of scheme 5-7 compound Si (15.5 g, 0.277 mol) in dry DMF (150 mL) was added NaH (12 g, 305 mol) at 0 °C slowly. After stirring at 0 °C for 1 h, BnBr (52 g, 305 mol) was added into the above mixture at 0°C. The reaction was stirred at room temperature for 16 h. Then the mixture was quenched with saturated aq. NH4C1 solution (150 mL) and then extracted with DCM (300 mL). The organic layer was washed with aq. LiC1 solution (150 mL x 3), dried over anhydrous Na2SO4 and concentrated. The residue was purified by column chromatography on silica gel (eluted with petroleum ether: ethyl acetate =100:0 to 100:1) to give the title compound (21 g, 53.1 % yield) as a colorless oil.
53.1%	Stage #1: Prop-2-ynyl alcohol With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; for 1h; Inert atmosphere; Stage #2: benzyl bromide In N,N-dimethyl-formamide; mineral oil at 0 - 20℃; for 16h; Inert atmosphere;	5.1 Step 1: ((Prop-2-ynyloxy)methyl)benzene (S2) Step 1: ((Prop-2-ynyloxy)methyl)benzene (S2) [0510] To a solution of scheme 5-7 compound SI (15.5 g, 0.277 mol) in dry DMF (150 mL) was added NaH (12 g, 305 mol) at 0 °C slowly. After stirring at 0 °C for 1 h, BnBr (52 g, 305 mol) was added into the above mixture at 0 °C. The reaction was stirred at room temperature for 16 h. Then the mixture was quenched with saturated aq. H4CI solution (150 mL) and then extracted with DCM (300 mL). The organic layer was washed with aq. LiCl solution (150 ml x3), dried over anhydrous Na2S04 and concentrated. The residue was purified by column chromatography on silica gel (eluted with petroleum ether: ethyl acetate =100:0 to 100: 1) to give the title compound (21 g, 53.1 % yield) as a colorless oil.
53.1%	Stage #1: Prop-2-ynyl alcohol With sodium hydride In N,N-dimethyl-formamide at 0℃; for 1h; Inert atmosphere; Stage #2: benzyl bromide In N,N-dimethyl-formamide at 0 - 20℃; for 16h; Inert atmosphere;	5.1 Step 1: ((prop-2-ynyloxy)methyl)benzene (S2) To a solution of scheme 5-7 compound S1 (15.5 g, 0.277 mol) in dry DMF (150 mL) was added NaH (12 g, 305 mol) at 0°C slowly. After stirring at 0°C for 1 hour, BnBr (52 g, 305 mol) was added into the mixture at 0°C. The reaction was stirred at room temperature for 16 hours. Then the mixture was quenched with saturated aq. NH4Cl solution (150 mL) and extracted with DCM (300 mL). The organic layer was washed with aq. LiCl solution (150 mL x 3), dried over anhydrous Na2SO4 and concentrated. The residue was purified by column chromatography on silica gel (eluted with petroleum ether: ethyl acetate =100:0 to 100:1) to afford the title compound (21 g, 53.1 % yield) as a colorless oil.
53.1%	Stage #1: Prop-2-ynyl alcohol With sodium hydride In N,N-dimethyl-formamide at 0℃; for 1h; Stage #2: benzyl bromide In N,N-dimethyl-formamide at 0 - 20℃; for 16h;	5.1 ((Prop-2-ynyloxy)methyl)benzene (S2) To a solution of Scheme 5-9 compound SI (15.5 g, 0.277 mol) in dry DMF (150 mL) was added NaH (12 g, 305 mol) at 0 °C slowly. After stirring at 0 °C for 1 h, BnBr (52 g, 305 mol) was added into the above mixture at 0 °C. The reaction was stirred at room temperature for 16 h. The mixture was quenched with saturated aq. H4CI solution (150 mL) and then extracted with DCM (300 mL). The organic layer was washed with aq. LiCl solution (150 mL X 3), dried over anhydrous Na2S04 and concentrated. The residue was purified by column chromatography on silica gel (eluted with petroleum ether: ethyl acetate =100:0 to 100: 1) to afford the title compound (S2) (21 g, 53.1 % yield) as a colorless oil.
53.1%	Stage #1: Prop-2-ynyl alcohol With sodium hydride In N,N-dimethyl-formamide at 0℃; for 1h; Stage #2: benzyl bromide In N,N-dimethyl-formamide at 0 - 20℃; for 16h;	5-10.1 Step 1: ((Prop-2-ynyloxy)methyl)benzene (S2) To a solution of propargyl alcohol (scheme 5-10 compound Si) (15.5 g, 0.277 mol) in dry DMF (150 mL) was slowly added NaH (12 g, 305 mol) at 0 °C. After stirring at 0 °C for 1 h, BnBr (52 g, 305 mol) was added into the above mixture at 0 °C. The reaction was stirred at room temperature for 16 h. The mixture was quenched with saturated aq. NH4C1 solution (150 mL) and then extracted with DCM (300 mL). The organic layer was washed with aq. LiC1 solution (150 mL x 3), dried over anhydrous Na2SO4 and concentrated. The residue was purified by column chromatography on silica gel (eluted with petroleum ether: ethyl acetate =100:0 to 100:1) to afford Scheme 5-10 compound S2 (21 g, 53.1 % yield) as a colorless oil.
53.1%	Stage #1: Prop-2-ynyl alcohol With sodium hydride In N,N-dimethyl-formamide at 0℃; for 1h; Stage #2: benzyl bromide In N,N-dimethyl-formamide at 0 - 20℃; for 16h;	1 Step 1: ((Prop-2-ynyloxy)methyl)benzene (S2) To a solution of scheme 5-7 compound S1 (15.5 g, 0.277 mol) in dry DMF (150 mL) was added NaH (12 g, 305 mol) at 0 oC slowly. After stirring at 0 oC for 1 h, BnBr (52 g, 305 mol) was added to the mixture at 0 oC. The reaction was stirred at room temperature for 16 h. Then the mixture was quenched with saturated aqeuous NH4Cl solution (150 mL) and extracted with DCM (300 mL). The organic layer was washed with aqeuous LiCl solution (150 mL x 3), dried over anhydrous Na2SO4,and concentrated. The residue was purified by column chromatography on silica gel (eluted with petroleum ether: ethyl acetate =100:0 to 100:1) to afford the title compound (21 g, 53.1 % yield) as a colorless oil.
	Stage #1: Prop-2-ynyl alcohol With N,N,N-tributyl-1-butanaminium iodide; sodium hydride In N,N-dimethyl-formamide at 20℃; for 0.5h; Stage #2: benzyl bromide With ammonia hydrochloride In N,N-dimethyl-formamide at 20℃; for 16h;	To a solution of 3 -prop- 1 -ol ( 1.17 g, 11.88 mmol) in anhydrous DMF ( 10OmL) under nitrogen atmosphere was added TBAI (0.87 g, 2.38 mmol) followed by 60% NaH dispersion in oil (0.55g, 14.26 mmol) in portions over 0.5h. The reaction mixture was stirred for 0.5hr at which time benzyl bromide (2.44g, 14.26 mmol) was added by syringe. The reaction EPO mixture was stirred for 16h at room temperature at which time the reaction was quenched by the addition of sat. aq. NH4Cl (10OmL). The reaction mixture was transferred to separatory funnel and extracted with ether (3x75mL). The combined organic extracts were washed with water (5OmL), brine (75mL), dried (Na2SO4), filtered and the solvent removed under vacuum. The residue was purified by MPLC (silica column) with stepwise gradient elution (0 - 60% EtOAc/hexanes as eluent) to afford the title compound (i-56).Intermediates related to those described above of varying substitution and alkyl chain length may be prepared from the appropriate starting materials using the procedures described above.
	With sodium hydride In tetrahydrofuran
	With tetrabutylammonium bromide; sodium hydroxide In water monomer; toluene at 50℃; for 4h;
	Stage #1: Prop-2-ynyl alcohol With potassium hydroxide In dimethyl sulfoxide at 0℃; Inert atmosphere; Stage #2: benzyl bromide In dimethyl sulfoxide at 0 - 20℃; Inert atmosphere;
	Stage #1: Prop-2-ynyl alcohol With sodium hydride In tetrahydrofuran; mineral oil at 0 - 20℃; for 1h; Inert atmosphere; Stage #2: benzyl bromide In tetrahydrofuran; mineral oil Inert atmosphere;
	With potassium hydroxide In dimethyl sulfoxide at 0 - 20℃;
	With sodium hydride In tetrahydrofuran at 22℃; for 3h; Inert atmosphere;
	Stage #1: Prop-2-ynyl alcohol With sodium hydride In N,N-dimethyl-formamide at 0℃; for 0.5h; Stage #2: benzyl bromide In N,N-dimethyl-formamide at 0 - 20℃; for 12h;

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[7]Sugimoto, Tetsuya; Ishihara, Jun; Murai, Akio [Synlett, 1999, # 5, p. 541 - 544]
[8]Current Patent Assignee: NOVARTIS AG; Novartis (w/o Sandoz) - WO2003/84941, 2003, A2 Location in patent: Page/Page column 21
[9]Achard, Thierry; Lepronier, Aymeric; Gimbert, Yves; Clavier, Herve; Giordano, Laurent; Tenaglia, Alphonse; Buono, Gerard [Angewandte Chemie - International Edition, 2011, vol. 50, # 15, p. 3552 - 3556]
[10]Bian, Qinghua; Li, Fengqi; Li, Shuoning; Ma, Sijie; Walsh, Patrick J.; Wang, Lifeng; Wang, Min; Zhong, Jiangchun; Zhou, Yun [Synlett, 2020, vol. 31, # 1, p. 60 - 64]
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6
[ 4039-82-1 ]
[ 100-52-7 ]
4-(benzyloxy)-1-phenylbut-2-yn-1-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87%	Stage #1: Benzyl propargyl ether With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.333333h; Stage #2: benzaldehyde In tetrahydrofuran; hexane at -78 - 20℃; for 3.5h;
80%	Stage #1: Benzyl propargyl ether With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 2.5h; Stage #2: benzaldehyde In tetrahydrofuran; hexane at -78 - 25℃; for 1.5h; Stage #3: With ammonium chloride In tetrahydrofuran; hexane; water	4.2.3. General procedure for the synthesis of 4-(benzyloxy)-1-phenylbut-2-yn-1-ol derivatives General procedure: n-BuLi (1 mmol, 1.6 M in hexane) was added dropwise to a solution of propargyl benzyl ether (1.0 mmol) in freshly dried THF (10 mL) at -78 °C. The reaction mixture was stirred at -78 °C for 2.5 h, after that aldehyde (1.0 mmol) in dry THF (1 mL) was added dropwise. The reaction mixture was further stirred at the same temperature for 1 h and then allowed to warm to 25 °C over 30 min. After completion of reaction (by TLC) saturated aqueous NH4Cl (10 mL) was added and the mixture was extracted with EtOAc (3 × 20 mL). The combined organic layers were dried over Na2SO4, filtered, and the solvent was evaporated in vacuo. The obtained crude product was purified by flash column chromatography over silica gel, eluting with step gradient of hexane/EtOAc to afford pure 1-Aryl-4-benzyloxybut-2-yn-1-ol derivatives 4b-k with 70-80% yield. The reference compound 4a was synthesized from the starting compound benzyl alcohol using the same procedure.
80%	Stage #1: Benzyl propargyl ether With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: benzaldehyde In tetrahydrofuran; hexane at -78 - 20℃; for 2h; Inert atmosphere;

	With base
	Stage #1: Benzyl propargyl ether With n-butyllithium In tetrahydrofuran at -78℃; for 0.666667h; Inert atmosphere; Stage #2: benzaldehyde In tetrahydrofuran at -78℃; Inert atmosphere;
	With n-butyllithium In tetrahydrofuran at -78 - 20℃; Inert atmosphere;	II. Preparation of Alkynone Substrates General procedure: To a solution of arylalkyne (2.4 mmol, 1.2 equiv.) in dry THF (6 mL), n-BuLi(0.88 mL, 2.2 mmol, 1.1 equiv.) was added at -78 oC under Ar. The reactionmixture was allowed to warm to 0 oC and stirred at 0 oC for 0.5 h. Then thereaction mixture was cooled to -78 oC again. Add a THF solution ofarylaldehyde (2.0 mmol, 1.0 equiv.) to the mixture at -78 oC and stir the mixturefor 0.5 h. The reaction mixture was warmed to room temperature and stirreduntil aldehydes disappeared monitored by TLC. Then the reaction wasquenched by saturated NH4Cl solution and extracted with ethyl acetate. Thecombined organic layers were washed with brine, dried over anhydrousNa2SO4 and concentrated under reduced pressure to give a residue. Finally, theresidue was purified through column chromatography on silical gel with2petroleum ether and ethyl acetate to give the pure product.[1]

Reference： [1]Nakano, Takeo; Soeta, Takahiro; Endo, Kohei; Inomata, Katsuhiko; Ukaji, Yutaka [Journal of Organic Chemistry, 2013, vol. 78, # 24, p. 12654 - 12661]
[2]Location in patent: experimental part Reddy, Nimmanapalli P.; Chandramohan Reddy; Aparoy, Polamarasetty; Achari, Chandrani; Sridhar, P. Ramu; Reddanna, Pallu [European Journal of Medicinal Chemistry, 2012, vol. 47, # 1, p. 351 - 359]
[3]Zhen, Long; Yuan, Kun; Li, Xiu-Yan; Zhang, Chenyun; Yang, Jun; Fan, Hui; Jiang, Liqin [Organic Letters, 2018, vol. 20, # 10, p. 3109 - 3113]
[4]Zhou; Green [Tetrahedron Letters, 1993, vol. 34, # 28, p. 4497 - 4500]
[5]Raji Reddy, Chada; Vijaykumar, Jonnalagadda; Jithender, Enukonda; Reddy, Gangireddy Pavan Kumar; Gree, Rene [European Journal of Organic Chemistry, 2012, # 29, p. 5767 - 5773]
[6]Zhai, Lele; Yang, Zhigang; Man, Qinghong; Yang, Mingyu; Ren, Yangqing; Wang, Lei; Li, Huilin; She, Xuegong [Tetrahedron Letters, 2022, vol. 91]

7
[ 4039-82-1 ]
[ 75-07-0 ]
[ 171011-84-0 ]

Yield	Reaction Conditions	Operation in experiment
88%	Stage #1: Benzyl propargyl ether With LDSA In tetrahydrofuran at 20℃; for 0.333333h; Stage #2: acetaldehyde In tetrahydrofuran at -80 - 20℃; for 10h;
88%	With lithium diisopropyl amide In tetrahydrofuran at 0℃; for 6h;
	With base

Reference： [1]Leuser, Helena; Perrone, Sylvie; Liron, Frederic; Kneisel, Florian F.; Knochel, Paul [Angewandte Chemie - International Edition, 2005, vol. 44, # 29, p. 4627 - 4631]
[2]Sravanth Kumar; Praneeth; Srihari; Yadav [Tetrahedron Letters, 2017, vol. 58, # 6, p. 509 - 511]
[3]Zhou; Green [Tetrahedron Letters, 1993, vol. 34, # 28, p. 4497 - 4500]

8
[ 4039-82-1 ]
[ 4094-90-0 ]

Yield	Reaction Conditions	Operation in experiment
83%	With iodine; sodium methylate In methanol at 20℃;
64%	With tert.-butylhydroperoxide; potassium iodide In methanol; water at 20℃; for 6h;
	With ethylmagnesium bromide; iodine 1.) THF, RT, 1 h, 2.) THF, 30 min; Yield given. Multistep reaction;

	With dmap; iodine In dichloromethane for 6h; Reflux;
	With copper(l) iodide; iodine; β‐cyclodextrin In water at 20℃; for 0.5h; Green chemistry;	General procedure for the synthesis of 1,4-disubstituted-1,2,3-triazoles (3a-3n & 4a-4n) General procedure: A suspension of phenylacetylene 1 (50mg, 1.0mmol) and iodine (124mg, 1.5mmol) was added to a mixture of CuI (10mol %) and β-cyclodextrin (1.0mol %) dissolved in water (5mL) and stirred for 30minat room temperature. A red homogeneous solution was formed, which confirmed the formation of 1-iodophenylacetylene as revealed by TLC analysis. Thereafter, benzyl bromide 2 (84mg, 1.0mmol) and sodium azide (64mg, 2.0mmol) were added to the reaction mixture and reaction temperature raised up to 90°C for 4h. After completion of reaction as monitored by TLC, the reaction mixture was diluted with water (20mL). The aqueous solution was extracted with EtOAc (3×10mL) and combined organic layer was washed with saturated Na2S2O3 solution, dried over anhydrous Na2SO4, and evaporated in vacuum. The residue was purified by column chromatography using (10% EtOAc: petroleum ether) to afford the desired product.

Reference： [1]Xu, Wei; Chen, Qing-Yun [Journal of Organic Chemistry, 2002, vol. 67, # 26, p. 9421 - 9427]
[2]Rajender Reddy; Venkateshwar; Uma Maheswari; Santhosh Kumar [Tetrahedron Letters, 2010, vol. 51, # 16, p. 2170 - 2173]
[3]Narayana Rao; Periasamy [Synthetic Communications, 1995, vol. 25, # 15, p. 2295 - 2299]
[4]Liu, Hui; Chen, Chen; Wang, Limin; Tong, Xiaofeng [Organic Letters, 2011, vol. 13, # 19, p. 5072 - 5075]
[5]Dheer, Divya; Rawal, Ravindra K.; Singh, Virender; Sangwan; Das, Parthasarathi; Shankar, Ravi [Tetrahedron, 2017, vol. 73, # 30, p. 4295 - 4306]

9
[ 4039-82-1 ]
[ 67515-49-5 ]

Yield	Reaction Conditions	Operation in experiment
82%	With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 3h;
82%	In tetrahydrofuran at 20℃; for 3h;
82%	With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 3h; Inert atmosphere;

82%	With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 1h; Inert atmosphere;
77%	With potassium <i>tert</i>-butylate In dimethyl sulfoxide for 0.05h; microwave irradiation;
69%	With potassium <i>tert</i>-butylate In N,N-dimethyl-formamide at 70℃; for 24h;
68%	With potassium <i>tert</i>-butylate In toluene at 100℃; for 1h;
66.3%	With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 3h; Inert atmosphere;	5.2 Step 2: ((Propa-l,2-dienyloxy)methyl)benzene (S3) [0475] To a solution of Scheme 5-7 compound S2 (21 g, 0.144 mol) in dry THF (120 ml) was added t-BuOK (4.84 g, 0.0432 mol). The reaction mixture was stirred at room temperature for 3 h and then concentrated under reduced pressure. Et20 (200 mL) was added and the resulting mixture was filtered. The filtrate was concentrated and purified by column chromatography on silica gel (eluted with petroleum ether) to afford the title compound (13.8 g, 66.3 % yield) as a colorless oil.
66.3%	With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 3h;	5.2 Step 2: ((Propa-i,2-dienyloxy)methyl)benzene (S3) To a solution of scheme 5-7 compound S2 (21 g, 0.144 mol) in dry THF (120 ml) was added t-BuOK (4.84 g, 0.0432 mol). The reaction mixture was stirred at room temperature for 3 h and then concentrated under reduced pressure. Et20 (200 mL) was added and the resulting mixture was filtered. The filtrate was concentrated and purified by column chromatography on silica gel (eluted with petroleum ether) to give the title compound (13.8 g, 66.3 % yield) as a colorless oil.
66.3%	With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 3h; Inert atmosphere;	5.2 ((Propa-l,2-dienyloxy)methyl)benzene (S3) ((Propa-l,2-dienyloxy)methyl)benzene (S3) [0511] To a solution of scheme 5-7 compound S2 (21 g, 0.144 mol) in dry THF (120 ml) was added t-BuOK (4.84 g, 0.0432 mol). The reaction mixture was stirred at room temperature for 3 h and then concentrated under reduced pressure. Et20 (200 mL) was added and the resulting mixture was filtered. The filtrate was concentrated and purified by column chromatography on silica gel (eluted with petroleum ether) to give the title compound (13.8 g, 66.3 % yield) as a colorless oil.
66.3%	With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 3h; Inert atmosphere;	5.2 Step 2: ((propa-1,2-dienyloxy)methyl)benzene (S3) To a solution of scheme 5-7 compound S2 (21 g, 0.144 mol) in dry THF (120 ml) was added t-BuOK (4.84 g, 0.0432 mol). The reaction mixture was stirred at room temperature for 3 hours and then concentrated under reduced pressure. Et2O (200 mL) was added and the resulting mixture was filtered. The filtrate was concentrated and purified by column chromatography on silica gel (eluted with petroleum ether) to afford the title compound (13.8 g, 66.3 % yield) as a colorless oil.
66.3%	With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 3h;	5.2 ((Propa-l,2-dienyloxy)methyl)benzene (S3) To a solution of Scheme 5-9 compound S2 (21 g, 0.144 mol) in dry THF (120 ml) was added t-BuOK (4.84 g, 0.0432 mol). The reaction mixture was stirred at room temperature for 3 h and then concentrated under reduced pressure. EfeO (200 mL) was added and the resulting mixture was filtered. The filtrate was concentrated and purified by column chromatography on silica gel (eluted with petroleum ether) to afford the title compound (S3) (13.8 g, 66.3 % yield) as a colorless oil.
66.3%	With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 3h;	5-10.2 Step 2: ((Propa-i,2-dienyloxy)methyl)benzene (S3) To a solution of Scheme 5-10 compound S2(21 g, 0.144 mol) in dry THF (120 ml) was added t-BuOK (4.84 g, 0.0432 mol). The reaction was stirred at room temperature for 3 h and then concentrated under reduced pressure. Et20 (200 mL) was added and the resulting mixture was filtered. The filtrate was concentrated and purified by column chromatography on silica gel (eluted with petroleum ether) to afford Scheme 5-10 compound S3 (13.8 g, 66.3 % yield) as a colorless oil.
66.3%	With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 3h;	2 Step 2: ((Propa-1,2-dienyloxy)methyl)benzene (S3) To a solution of scheme 5-7 compound S2 (21 g, 0.144 mol) in dry THF (120 ml) was added t-BuOK (4.84 g, 0.0432 mol). The reaction mixture was stirred at room temperature for 3 h and then concentrated under reduced pressure. Et2O (200 mL) was added and the resulting mixture was filtered. The filtrate was concentrated and purified by columnchromatography on silica gel (eluted with petroleum ether) to afford the title compound (13.8 g, 66.3 % yield) as a colorless oil.
	With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 1h; Inert atmosphere;
	With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; Inert atmosphere; Schlenk technique;
	With potassium <i>tert</i>-butylate In tetrahydrofuran Inert atmosphere;
	With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; Inert atmosphere;
	With potassium <i>tert</i>-butylate In tetrahydrofuran at 0 - 20℃; for 3h;
	With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃;
	With potassium <i>tert</i>-butylate In tetrahydrofuran at 22℃; for 3h; Inert atmosphere;
	With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 1h;

Reference： [1]Trost, Barry M.; Xie, Jia [Journal of the American Chemical Society, 2006, vol. 128, # 18, p. 6044 - 6045]
[2]Trost, Barry M.; Xie, Jia [Journal of the American Chemical Society, 2008, vol. 130, # 19, p. 6231 - 6242]
[3]Trost, Barry M.; Xie, Jia; Sieber, Joshua D. [Journal of the American Chemical Society, 2011, vol. 133, # 50, p. 20611 - 20622]
[4]Tap, Aurélien; Lecourt, Camille; Dhambri, Sabrina; Arnould, Mathieu; Galvani, Gilles; Nguyen Van Buu, Olivier; Jouanneau, Morgan; Férézou, Jean-Pierre; Ardisson, Janick; Lannou, Marie-Isabelle; Sorin, Geoffroy [Chemistry - A European Journal, 2016, vol. 22, # 14, p. 4938 - 4944]
[5]Moghaddam, Firouz Matloubi; Emami, Rahdar [Synthetic Communications, 1997, vol. 27, # 23, p. 4073 - 4077]
[6]Inamoto, Kiyofumi; Yamamoto, Akio; Ohsawa, Kazutoshi; Hiroya, Kou; Sakamoto, Takao [Chemical and Pharmaceutical Bulletin, 2005, vol. 53, # 11, p. 1502 - 1507]
[7]Helms, Matthias; Schade, Wolfgang; Pulz, Robert; Watanabe, Toshiko; Al-Harrasi, Ahmed; Fisera, Lubor; Hlobilova, Iva; Zahn, Gernot; Reissig, Hans-Ulrich [European Journal of Organic Chemistry, 2005, # 6, p. 1003 - 1019]
[8]Current Patent Assignee: ASTRAZENECA PLC; MEDCHEM DISCOVERY CONSULTING - WO2017/35405, 2017, A1 Location in patent: Paragraph 0475
[9]Current Patent Assignee: ASTRAZENECA PLC - WO2017/35411, 2017, A1 Location in patent: Paragraph 0561
[10]Current Patent Assignee: ASTRAZENECA PLC - WO2017/35413, 2017, A2 Location in patent: Paragraph 0511
[11]Current Patent Assignee: ASTRAZENECA PLC - WO2017/35415, 2017, A1 Location in patent: Paragraph 0566; 0598; 0600
[12]Current Patent Assignee: ASTRAZENECA PLC; MEDCHEM DISCOVERY CONSULTING - WO2017/35401, 2017, A1 Location in patent: Paragraph 0486
[13]Current Patent Assignee: ASTRAZENECA PLC - WO2017/35417, 2017, A1 Location in patent: Paragraph 0604
[14]Current Patent Assignee: ASTRAZENECA PLC - WO2017/35409, 2017, A1 Location in patent: Paragraph 0613
[15]Kona, Chandrababu Naidu; Ramana, Chepuri V. [Chemical Communications, 2014, vol. 50, # 17, p. 2152 - 2154]
[16]De la Campa, Raquel; Flrez, Josefa [Chemistry - A European Journal, 2015, vol. 21, # 5, p. 1854 - 1859]
[17]Lippincott, Daniel J.; Linstadt, Roscoe T. H.; Maser, Michael R.; Lipshutz, Bruce H. [Angewandte Chemie - International Edition, 2017, vol. 56, # 3, p. 847 - 850][Angew. Chem., 2017, vol. 129, p. 865 - 868]
[18]Bernar, Ivan; Fiser, Béla; Blanco-Ania, Daniel; Gómez-Bengoa, Enrique; Rutjes, Floris P. J. T. [Organic Letters, 2017, vol. 19, # 16, p. 4211 - 4214]
[19]Parisotto, Stefano; Palagi, Lorenzo; Prandi, Cristina; Deagostino, Annamaria [Chemistry - A European Journal, 2018, vol. 24, # 21, p. 5484 - 5488]
[20]Lippincott, Daniel J.; Linstadt, Roscoe T. H.; Maser, Michael R.; Gallou, Fabrice; Lipshutz, Bruce H. [Organic Letters, 2018, vol. 20, # 16, p. 4719 - 4722]
[21]Pozo, Juan Del; Zhang, Shaochen; Romiti, Filippo; Xu, Shibo; Conger, Ryan P.; Hoveyda, Amir H. [Journal of the American Chemical Society, 2020, vol. 142, # 42, p. 18200 - 18212]
[22]Wang, Jun; Yang, Zhiping [Angewandte Chemie - International Edition, 2021, vol. 60, # 52, p. 27288 - 27292][Angew. Chem., 2021, vol. 133, # 52, p. 27494 - 27498]

10
[ 4039-82-1 ]
[ 218431-34-6 ]

Yield	Reaction Conditions	Operation in experiment
96%	With N-Bromosuccinimide; silver nitrate In acetone for 1h;
89%	With N-Bromosuccinimide; silver nitrate In acetone at 24℃; for 0.5h; Inert atmosphere; Darkness;
85%	With N-Bromosuccinimide; 1,8-diazabicyclo[5.4.0]undec-7-ene In acetonitrile at 20℃; for 0.166667h; Green chemistry;

82%	With N-Bromosuccinimide; silver nitrate In acetone at 20℃; for 2h;
68%	With N-Bromosuccinimide; silver nitrate In acetone at 24℃; for 3h;
37%	With potassium hydroxide; 18-crown-6 ether; carbon tetrabromide In benzene for 2h; Ambient temperature;

Reference： [1]Yang, Xiaobao; Zhu, Li; Zhou, Yuedong; Li, Zhong; Zhai, Hongbin [Synthesis, 2008, # 11, p. 1729 - 1732]
[2]Location in patent: experimental part Hwang, Soonho; Kang, Hee Ryong; Kim, Sanghee; Haze, Olesya; Danheiser, Rick L. [Organic Syntheses, 2009, vol. 86, p. 225 - 235]
[3]Li, Mengru; Li, Yueju; Zhao, Baozhong; Liang, Fushun; Jin, Long-Yi [RSC Advances, 2014, vol. 4, # 57, p. 30046 - 30049]
[4]Kim, Sanghee; Kim, Shinae; Lee, Taeho; Ko, Hyojin; Kim, Deukjoon [Organic Letters, 2004, vol. 6, # 20, p. 3601 - 3604]
[5]He, Lu-Ying; Schulz-Senft, Mathias; Thiedemann, Birk; Linshoeft, Julian; Gates, Paul J.; Staubitz, Anne [European Journal of Organic Chemistry, 2015, vol. 2015, # 11, p. 2498 - 2502]
[6]Abele, Edgars; Rubina, Kira; Abele, Ramona; Gaukhman, Aleksandr; Lukevics, Edmunds [Journal of Chemical Research - Part S, 1998, # 9, p. 618 - 619]

11
[ 14073-97-3 ]
[ 4039-82-1 ]
(1S,2S,5R)-2-i-propyl-5-methyl-1-(3-benzyloxy-1-propyn-1-yl)cyclohexan-1-ol [ No CAS ]
(1R,2S,5R)-2-i-propyl-5-methyl-1-(3-benxyloxy-1-propyn-1-yl)cyclohexan-1-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
96%	Stage #1: Benzyl propargyl ether With n-butyllithium; cerium(III) chloride In tetrahydrofuran at -78℃; for 1h; Stage #2: (2R,5S)-menthone In tetrahydrofuran at -78℃; for 1h;
1: 96% 2: 4%	Stage #1: Benzyl propargyl ether With n-butyllithium In tetrahydrofuran at -78℃; for 1h; Stage #2: With cerium(III) chloride In tetrahydrofuran at 20℃; for 1h; Stage #3: (2R,5S)-menthone In tetrahydrofuran at -78℃; for 4h;

Reference： [1]Spino; Beaulieu; Lafreniere [Journal of Organic Chemistry, 2000, vol. 65, # 21, p. 7091 - 7097]
[2]Spino; Beaulieu; Lafreniere [Journal of Organic Chemistry, 2000, vol. 65, # 21, p. 7091 - 7097]

12
[ 4039-82-1 ]
[ 174953-30-1 ]
(S)-1-(phenylmethoxy)-2-hexyn-5-ol [ No CAS ]

Reference： [1]Synthetic Communications,2003,vol. 33,p. 633 - 640

13
[ 609-14-3 ]
[ 4039-82-1 ]
ethyl 2-acetyl-2-methyl-3-methylene-4-benzyloxybutanoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With indium(III) triflate; triethylamine at 80℃; for 22h;
80%	With triethylamine In tetrahydrofuran at 80℃; for 22h;
80%	at 80℃; for 22h;

Reference： [1]Location in patent: scheme or table Fujimoto, Taisuke; Endo, Kohei; Nakamura, Masaharu; Nakamura, Eiichi; Webster, Mark; Ragan, John A. [Organic Syntheses, 2009, vol. 86, p. 325 - 332]
[2]Nakamura, Masaharu; Endo, Kohei; Nakamura, Eiichi [Journal of the American Chemical Society, 2003, vol. 125, # 43, p. 13002 - 13003]
[3]Endo, Kohei; Hatakeyama, Takuji; Nakamura, Masaharu; Nakamura, Eiichi [Journal of the American Chemical Society, 2007, vol. 129, # 16, p. 5264 - 5271]

14
[ 4039-82-1 ]
[ 98-80-6 ]
[ 144479-03-8 ]

Yield	Reaction Conditions	Operation in experiment
92%	With caesium carbonate; triphenylphosphine; silver(l) oxide In dichloromethane at 35℃; for 3h; Inert atmosphere;	General procedure of Pd nanoparticles catalyzed oxidative cross-coupling reaction To 2 mL of CH2Cl2 were added 1 mmol of arylboronic acid and1.2 mmol of terminal alkyne, then 0.01 mmol of palladium nanoparticles(1 mol%), 0.1 mmol of PPh3 (10 mol%), 1 mmol of Ag2O and 2 mmol of Cs2CO3 were added in turn. The mixture was heated at 35 °C with stirring under a nitrogen atmosphere for the appropriate time (see Table 2, monitored by TLC or GC) till reaction was completed, then centrifuged. The solution was separated and the precipitate was washed with ether (5 mL x 3). The solutions were combined and washed with water, dried over anhydrous Na2SO4 and purified by column chromatography on silica gel with hexaneeethyl acetate (10:1) as eluent to yield the product. The precipitate was further washed sufficiently with methanol and ether, then dried, and the palladium nanoparticles were recovered.
87%	With potassium carbonate; silver(l) oxide In dichloromethane at 25℃;
71%	With silver tetrafluoroborate; (triphenylphosphine)gold(I) chloride; Selectfluor; triethylamine In acetonitrile at 50℃; for 12h; Inert atmosphere;

Reference： [1]Location in patent: experimental part Nie, Xiaopeng; Liu, Suli; Zong, Yan; Sun, Peipei; Bao, Jianchun [Journal of Organometallic Chemistry, 2011, vol. 696, # 8, p. 1570 - 1573]
[2]Zou, Gang; Zhu, Junru; Tang, Jie [Tetrahedron Letters, 2003, vol. 44, # 48, p. 8709 - 8711]
[3]Qian, Deyun; Zhang, Junliang [Beilstein Journal of Organic Chemistry, 2011, vol. 7, p. 808 - 812]

15
[ 695-06-7 ]
[ 4039-82-1 ]
1-benzyloxy-7-hydroxynon-2-yn-4-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	Stage #1: Benzyl propargyl ether With n-butyllithium In tetrahydrofuran at -78 - -30℃; Stage #2: hexan-4-olide With boron trifluoride diethyl etherate In tetrahydrofuran at -78 - 20℃; for 1h;

Reference： [1]Doubsky, Jan; Streinz, Ludvik; Saman, David; Zednik, Jiri; Koutek, Bohumir [Organic Letters, 2004, vol. 6, # 26, p. 4909 - 4911]

16
[ 4039-82-1 ]
[ 121-46-0 ]
exo-3-[2-(benzyloxy)ethylidene]tricyclo[3.2.1.0^2,4]oct-6-ene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	With (±)-cyclohexyl(phenyl)phosphine oxide In toluene at 25℃; for 50h;

Reference： [1]Bigeault, Julie; Giordano, Laurent; Buono, Gerard [Angewandte Chemie - International Edition, 2005, vol. 44, # 30, p. 4753 - 4757]

17
[ 4039-82-1 ]
[ 15448-47-2 ]
[ 174455-52-8 ]

Yield	Reaction Conditions	Operation in experiment
78%	Stage #1: Benzyl propargyl ether With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Stage #2: (R)-propylene oxide With boron trifluoride diethyl etherate In tetrahydrofuran; hexane at -78℃; for 1h; Further stages.;
76%	Stage #1: Benzyl propargyl ether With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Inert atmosphere; Stage #2: (R)-propylene oxide With boron trifluoride diethyl etherate In tetrahydrofuran; hexane at -78℃; Inert atmosphere;	(R)-6-(Benzyloxy)hex-4-yn-2-yl propionate ((R)-14). To a stirred solution of 13 (6.493 g, 44.41 mmol)in THF (250.0 mL) at -78 °C under Ar was added n-BuLi (2.5 M in hexanes, 21.3 mL, 53.25 mmol).After 30 min, BF3.Et2O (6.7 mL, 53.47 mmol) was added, followed by (R)-2-methyloxirane ((R)-7)(2.580 g, 44.41 mmol). Upon stirring at -78 °C overnight, the reaction was quenched with saturatedaqueous NH4Cl, extracted with ethyl acetate, washed with brine, dried over anhydrous Na2SO4,concentrated, and purified by flash chromatography on silica gel (hexanes:ethyl acetate = 30:1) to give(R)-14 as a pale yellow oil (6.895 g, 76%). [α]20D = 13.2 (c = 0.1, CHCl3).
76%	Stage #1: Benzyl propargyl ether With n-butyllithium In tetrahydrofuran at -78℃; for 0.5h; Inert atmosphere; Stage #2: (R)-propylene oxide With boron trifluoride diethyl etherate In tetrahydrofuran at -78℃; for 12h; Inert atmosphere;	2 The synthesis of compound (R)-11 is synthesized as follows Experimental procedure: A 500 mL one-neck round bottom flask was taken and 9 (6.5 g, 1.0 eq) and dry THF (220 mL) were added. Under Ar atmosphere, stir in a -78 ° C cold bath for 15 minutes, start adding nBuLi (21.3 mL, 1.2 eq) dropwise, add, The reaction was carried out at -78 ° C for about 30 minutes, and BF3·Et2O (6.7 mL, 1.2 eq) and (R)-10 (2.6 mL, 1.0 eq) were added dropwise, and the reaction was carried out at -78 ° C for about 12 hours. Work-up: quenched with saturated aqueous sodium bicarbonate and saturated aqueous ammonium chloride. Dry and concentrated with anhydrous sodium sulfate, and the residue was subjected to column chromatography to obtain 6.9 g, yield 76%.

64%

Stage #1: Benzyl propargyl ether With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Stage #2: (R)-propylene oxide With boron trifluoride diethyl etherate In tetrahydrofuran; hexane at -78℃; for 3h;

Reference： [1]Yadav, Jhillu S.; Gupta, Manoj K.; Prathap [Synthesis, 2007, # 9, p. 1343 - 1348]
[2]Sun, Zhi-Feng; Zhang, Tao; Liu, Jinyang; Du, Zhen-Ting; Zheng, Huaiji [Molecules, 2018, vol. 23, # 3]
[3]Current Patent Assignee: SHAANXI UNIVERSITY OF TECHNOLOGY; NORTHWEST A&F UNIVERSITY - CN108191655, 2018, A Location in patent: Paragraph 0080; 0092; 0126-0128
[4]Sharma; Reddy, K. Laxmi [Tetrahedron Asymmetry, 2006, vol. 17, # 23, p. 3197 - 3202]

18
[ 2461-42-9 ]
[ 4039-82-1 ]
1-(1-naphthalenyloxy)-3-(4-benzyloxymethyl-[1,2,3]triazol-1-yl)-propan-2-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With copper(l) iodide; sodium azide In various solvent(s) at 20℃; for 16h;

Reference： [1]Kumaraswamy, Gullapalli; Ankamma, Kukkadapu; Pitchaiah, Arigala [Journal of Organic Chemistry, 2007, vol. 72, # 25, p. 9822 - 9825]

19
[ 4039-82-1 ]
[ 13807-91-5 ]

Reference： [1]Synthesis,1987,p. 1007 - 1009

20
[ 4039-82-1 ]
[ 17274-65-6 ]
[ 717139-86-1 ]

Yield	Reaction Conditions	Operation in experiment
75%	With piperidine; tri-tert-butyl phosphine; copper(I) iodide In hexane at 50℃; for 20h;	E 12 Preparation of {2-[5-(3-benzyloxy-prop-1-ynyl)-1H-indol-3-yl]-ethyl}-dimethyl-amine Preparation of {2- [5- (3-BENZYLOXY-PROP-1- YNYL)-1H-INDOL-3-YL]-ETHYL}-DIMETHYL-AMINE : A Schlenk flask is charged with Cul (19 mg, 0.1 MMOL), Pd (PhCN) 2CI2 (39 mg, 0.1 mmol), piperidine (28 mL), and [2- (5-BROMO-1H-INDOL-3-YL)-ETHYL]-DIMETHYL-AMINE (EXAMPLE 3) (2.70 g, 10 MMOL). The mixture is degassed, and then 0.4 mL of a solution of P (TBU) 3 in hexane (0.2 MMOL) is added. The stirred yellow solution is warmed to 50C, and a solution of benzyl propargyl ether (2.65 g, 20 MMOL) in piperidine (2 mL) is added during a 5 hour period. The yellow reaction mixture is left stirring for another 15 hours when HPLC indicates complete conversion of the 5-bromotryptamine. The mixture is diluted with ethyl acetate, washed with brine (4 times 10%, 3 times saturated), and dried. After removal of the solvent, the residue is triturated with 20 mL hexane/O (I-PR) 2 (1: 1). The crystals which form are filtered off, washed with 4 mL of the same solvent mixture and dried in vacuo. Yield of the title compound: 2.70 g (75%), mp. = 93-95C.'H-NMR (CDCI3, 300 MHz) 5 2.36 (S, 6, N (CH3)2) ; 2.63-2. 70 (m, 2, CH2NME2) ; 2.90-2. 97 (m, 2, INDOL-CH2) ; 4.46 (s, 2, CH2-alkin) ; 4.72 (s, 2, CH2Ph) ; 6.94 (d, 1, J = 2.2 Hz, H-2); 7.18 (dd, 1, J = 8.4 Hz, J = 0.7 Hz, H-7); 7.26 (dd, 1, J = 1.4 Hz, H-6); 7.32, 7.37, 7.41 (m, 5, Ph p-, m-, o-H); 7.76 (d, 1, H-4); 8.63 (br s, 1, NH).

Reference： [1]Current Patent Assignee: BASF SE - WO2004/56769, 2004, A2 Location in patent: Page 52

21
[ 477742-97-5 ]
[ 4039-82-1 ]
[ 477742-99-7 ]

Yield	Reaction Conditions	Operation in experiment
37%	With copper(l) iodide; triethylamine; triphenylphosphine In acetonitrile at 50℃; for 12h;	4.4.3 5-{4-[3-(benzyloxy)prop-1-ynyl]phenyl}-1-ethyl-7,8-dimethoxy-1,3-dihydro-2H-1,4-benzodiazepin-2-one, IIbn. Stir for 12 hours under an inert atmosphere at 50° C., a mixture of 100 mg (0.27 mmol) of 5-(4-bromophenyl)-1-ethyl-7,8-dimethoxy-1,3-dihydro-2H-1,4-benzodiazepin-2-one (IIbl), 194 mg (1.3 mmol) of [(prop-2-ynyloxy)methyl]benzene, 9.0 mg of CuI, 5.2 mg of PdCl2, 18.0 mg of PPh3, 0.5 ml of TEA, 2 ml of CH3CN. Evaporate to dryness and purify by silica chromatography (AcOEt 1/hexane 1).Recrystallize in EtO2/pentane. Yield: 37%. M: 64-66° C. 1H-NMR (CDCl3, 300 MHz): d 1.12 (s, 3H, CH3), 3.72-3.83 (m, 4H, 1H CH2+OCH3), 4.00 (AB system,? d=0.63, JAB=13.5, 2H, -NCH2), 4.03 (s, 3H, OCH3), 4.43 (s, 2H, OCH2), 4.69 (m, 2H, =C-CH2), 4.77 (m, 1H, OCH2), 6.65 (s, 1H Ar), 6.86 (s, 1H Ar), 7.27-7.63 (m, 9H Ar).

Reference： [1]Current Patent Assignee: SYNTA PHARMACEUTICALS CORP. - US2004/152888, 2004, A1 Location in patent: Page/Page column 29-30

22
[ 4039-82-1 ]
[ 263351-43-5 ]
C₂₂H₂₅NO₃ [ No CAS ]

Reference： [1]Patent: US2005/256145,2005,A1 .Location in patent: Page/Page column 37

23
[ 4039-82-1 ]
[ 82543-16-6 ]
[ 1094603-82-3 ]

Yield	Reaction Conditions	Operation in experiment
92%	In tetrahydrofuran; at -20 - 50℃;	606.1 mmol of an alkali metal or alkaline earth metal alkoxide, preferably potassium tert-butoxide, are dissolved in 120 ml of tetrahydrofuran. A solution or suspension of 121.2 mmol of a compound of the formula I or II and 133.3 mmol of a propynol ether of the formula III in 520 ml of tetrahydrofuran is metered into the mixture at -20 to 50 C., preferably at 0 to 5 C. After reaction is complete, the reaction mixture is treated with 280 ml of water and subsequently rendered neutral by addition of acid, preferably acetic acid. The aqueous phase is separated off and discarded.The crude products obtained after evaporation of tetrahydrofuran are recrystallized from a suitable solvent and dried.; EXAMPLE 16beta,7beta;15beta,16beta-Dimethylene-17-(3-benzyloxypropynyl)androstane-3beta,5beta,17beta-triol (Vb)According to GWP1, 100 g (0.303 mol) of 3beta,5beta-dihydroxy-6beta,7beta;15beta,16beta-dimethyleneandrostan-17-one were reacted with 48.7 g (0.333 mol) of prop-1-yn-3-ol benzyl ether.The crude product was recrystallized from 700 ml of toluene. 133 g (0.279 mol) of 6beta,7beta;15beta,16beta-dimethylene-17alpha-(3-benzyloxypropynyl)androstane-3beta,5beta,11beta-triol=92% of theory were obtained.[alpha]D20=-70.1 (CHCl3, 12.15 mg in 1 ml of solution, T=20 C., d=100 mm).1H-NMR (400 MHz, CDCl3): delta=0.37-0.42 (1H, m, H-30 exo*), 0.63 (1H, td, J=9.0 Hz and 5.1 Hz, H-31 endo), 0.78 (1H q, J=5.1 Hz, H-31 endo), 0.82-0.88 (1H, m, H-6), 0.85 (3H, s, H-19), 0.91 (3H, s, H-18), 1.13 (1H, tt, J=8.4 Hz and 4.3 Hz, H-7), 1.15-1.27 (4H, m, H-30 exo, H-1, H-9, H-11), 1.39-1.44 (1H, m, H-2alpha), 1.46-1.54 (3H, m, H-11, H-12beta, H-15), 1.57 (1H, dt, J=13.6 Hz and 2.9 Hz, H-2beta), 1.66-1.74 (3H, m, H-12alpha, H-16, H-8), 1.84 (1H, td, J=14.5 Hz and 2.9 Hz, H-1beta), 1.96-2.01 (1H, m, H-4beta), 2.04 (1H, dd, J=12.1 Hz and 3.7 Hz, H-1), 2.23 (1H, dd, J=15.0 Hz and 3.3 Hz, H-4alpha), 2.15-2.35, 2.55-2.70, 3.25-3.50 (3H, strongly broadened, 3 times OH), 4.03 (1H, s, br., H-3), 4.30 (2H, s, H-22), 4.64 (2H, s, H-23), 7.29-7.38 (5H, m, H-25, H-26, H-27, H-28, H-29)13C-NMR (400 MHz, CDCl3): delta=8.97 (CH2, C-30), 11.69 (CH2, C-31), 15.20 (CH, C-7), 16.67 (CH, C-15), 18.26 (CH3, C-18), 19.04 (CH3, C-19), 21.79 (CH2, C-11), 25.34 (CH, C-6), 26.81 (CH2, C-1), 27.06 (CH, C-16), 27.69 (CH2, C-2), 34.20 (CH, C-8), 38.62 (CH2, C-12), 40.42 (C, C-10), 42.65 (C, C-13), 43.04 (CH2, C-4), 44.59 (CH, C-9), 52.88 (CH, C-14), 57.63 (CH2, C-22), 67.09 (CH, C-3), 71.59 (CH2, C-23), 74.84 (C, C-5), 79.80 (C, C-17), 82.06 (C, C-21), 88.99 (C, C-20), 127.93 (CH, C-27), 128.06 (CH, C-26, C-28), 128.44 (CH, C-25, C-29), 137.40 (C, C-24)MS (CI): m/e=476 (M+NH4-H2O)+, 459 (M+H-H2O)+, 441 (459-H2O), 348 (M+NH4-C10H10O)+, 331 (476-C10H9O), 313 (331-H2O), 295 (313-H2O), 164 (C11H16O+), 91 (C7H7+)IR: v=3390 (O-H, stretching oscillation of alcohols), 3088, 3018 (C-H, stretching oscillation of aromatic and olefinic hydrocarbon), 2937, 2867 (C-H, stretching oscillation of aliphatic hydrocarbon), 2225 (C-C, stretching oscillation of alkyne), 1052 (C-O, stretching oscillation of alcohols), 739 (C-H, deformation oscillation of aromatic or olefinic hydrocarbon)

Reference： [1]Patent: US2009/12286,2009,A1 .Location in patent: Page/Page column 5

24
[ 50-00-0 ]
[ 4039-82-1 ]
((buta-2,3-dien-1-yloxy)methyl)benzene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86%	With N-cyclohexyl-cyclohexanamine; copper(I) bromide In 1,4-dioxane at 150℃; for 0.216667h; Microwave irradiation;
81%	With copper(l) iodide; N-cyclohexyl-cyclohexanamine In 1,4-dioxane for 1.5h; Inert atmosphere; Reflux;
75%	With copper(l) iodide; diisopropylamine In 1,4-dioxane at 110℃; for 12.5h;

70%	With diisopropylamine; copper(I) bromide In 1,4-dioxane for 18h; Inert atmosphere; Reflux;
	With copper(l) iodide; N-cyclohexyl-cyclohexanamine In 1,4-dioxane Reflux; Inert atmosphere;

Reference： [1]Location in patent: body text Nakamura, Hiroyuki; Sugiishi, Tsuyuka; Tanaka, Yuko [Tetrahedron Letters, 2008, vol. 49, # 50, p. 7230 - 7233]
[2]Kuang, Jinqiang; Shengming, Ma. [Journal of Organic Chemistry, 2009, vol. 74, # 4, p. 1763 - 1765]
[3]Luo, Hongwen; Ma, Shengming [European Journal of Organic Chemistry, 2013, # 15, p. 3041 - 3048]
[4]Hayashi, Naoki; Hirokawa, Yusuke; Shibata, Ikuya; Yasuda, Makoto; Baba, Akio [Organic and Biomolecular Chemistry, 2008, vol. 6, # 11, p. 1949 - 1954]
[5]Snead, Russell F.; Nekvinda, Jan; Santos, Webster L. [New Journal of Chemistry, 2021, vol. 45, # 33, p. 14925 - 14931]

25
[ 4039-82-1 ]
[ 90794-29-9 ]
[ 1095548-87-0 ]

Reference： [1]Organic Letters,2009,vol. 11,p. 229 - 231

26
[ 941-55-9 ]
[ 4039-82-1 ]
[ 1135539-04-6 ]

Yield	Reaction Conditions	Operation in experiment
92%	With methyl-phenyl-thioether; copper(I) bromide In water at 25℃; for 16h; regioselective reaction;
90%	With copper(II) acetate monohydrate; 2-amino-phenol In acetonitrile at 20℃; for 0.5h; regioselective reaction;	4.2. A Typical procedure for the preparation of ring-product 4-phenyl-1-(toluene-4-sulfonyl)-1H-[1,2,3]triazole (3a) General procedure: To a stirred solution of phenylacetylene (1a, 112 mg, 1.1 mmol), 4-methylbenzenesulfonyl azide (2a, 197 mg, 1 mmol), and 2-aminophenol (8a, 5.5 mg, 0.05 mmol) in MeCN (1 mL) was added Cu(OAc)2·H2O (20 mg, 0.1 mmol) at room temperature. After 2a was exhausted (ca. 20 min, monitored by TLC), the solvent was removed off in vacuum. The residue was purified by chromatography (silica gel, 10% EtOAc in PE) to give desired product 3a as a colorless solid (284 mg, 95%).

Reference： [1]Wang, Feng; Fu, Hua; Jiang, Yuyang; Zhao, Yufen [Advanced Synthesis and Catalysis, 2008, vol. 350, # 11-12, p. 1830 - 1834]
[2]Location in patent: experimental part Liu, Yantao; Wang, Xinyan; Xu, Jimin; Zhang, Qun; Zhao, Yi; Hu, Yuefei [Tetrahedron, 2011, vol. 67, # 34, p. 6294 - 6299]

27
[ 4039-82-1 ]
[ 219631-28-4 ]

Yield	Reaction Conditions	Operation in experiment
98%	With copper(l) iodide; nickel(II) chloride hexahydrate; N,N,N,N,-tetramethylethylenediamine; oxygen In tetrahydrofuran at 20℃;
98%	With copper(l) iodide; ethyl 2,2-dibromoacetoacetate; triethylamine In dichloromethane at 20℃; for 24h;	4.4. General procedure for homo-coupling of alkynes General procedure: Ethyl α,α-dibromoacetoacetate 2a (46.1 mg, 0.16 mmol,30 mol %), alkynes 1a-v(0.55 mmol, 1.0 equiv), CuI (30.5 mg,0.16 mmol, 30 mol %), and triethylamine (0.15 mL, 1.1 mmol,2.0 equiv) were added under ambient temperature to 2 mL of CH2Cl2in air. After stirred at room temperature for the appropriate time (monitored by TLC), the reaction was quenched by addition of H2O (3 mL) and then extracted with ethyl acetate (33 mL). The combined organic layer was washed with brine, dried over Na2SO4,and concentrated. The crude product was purified by column chromatography on silica gel with mixture of petroleum ether and ethyl acetate as eluent to afford the corresponding products 3a-v
92%	With copper(l) iodide; perfluorobutanesulfonyl azide; 1,8-diazabicyclo[5.4.0]undec-7-ene In chloroform at 20℃; for 0.166667h;

86%	With triethylamine In dichloromethane at 40℃; for 36h; Schlenk technique;
79%	With N,N'-di-tert-butyldiaziridinone; copper(I) bromide In acetonitrile at 20℃; for 2h;
70%	With oxygen; 1,8-diazabicyclo[5.4.0]undec-7-ene; copper dichloride In tetrahydrofuran at 20℃; for 24h; Air atmosphere;
69%	With Co(salen)complex; N,N'-di-tert-butyldiaziridinone In ethyl acetate at 80℃; for 6h; Schlenk technique; Inert atmosphere;	Cobalt-Catalyzed Homocoupling Reaction; General Procedure General procedure: To a flame-dried Schlenk tube with a stir bar was added Co(salen)complex 4 (10 mol%). The contents were evacuated and backfilledwith N2 (3 ×). Di-tert-butyldiaziridinone (2; 0.3 mmol) and alkyne(0.2 mmol) were added via microinjection syringe dissolved in anhydEtOAc (0.2 M). The mixture was stirred at 80 °C (oil bath). When thereaction was complete (TLC monitoring), the mixture was directlyconcentrated by rotary evaporation. The coupling products wereisolated by column chromatography (silica gel, typically 0-30%EtOAc/PE)
	Multi-step reaction with 2 steps 1: N-Bromosuccinimide; silver nitrate / acetone / 0.5 h / 24 °C / Inert atmosphere; Darkness 2: copper(l) iodide; bis-triphenylphosphine-palladium(II) chloride; diisopropylamine / tetrahydrofuran / 1 h / 30 °C / Inert atmosphere

Reference： [1]Yin, Weiyan; He, Chuan; Chen, Mao; Zhang, Heng; Lei, Aiwen [Organic Letters, 2009, vol. 11, # 3, p. 709 - 712]
[2]Fan, Xiaohui; Li, Na; Shen, Tong; Cui, Xiao-Meng; Lv, Hao; Zhu, Hong-Bo; Guan, Yong-Hong [Tetrahedron, 2014, vol. 70, # 2, p. 256 - 261]
[3]Suárez, José Ramón; Collado-Sanz, Daniel; Cárdenas, Diego J.; Chiara, Jose Luis [Journal of Organic Chemistry, 2015, vol. 80, # 2, p. 1098 - 1106]
[4]Zhang, Yuanteng; Wu, Yong; Su, Yaqiong; Cao, Yue; Liang, Zhenjin; Yang, Dali; Yu, Ruohan; Zhang, Dongchao; Wu, Jinsong; Xiao, Wei; Lei, Aiwen; Gu, Dong [Small, 2022, vol. 18, # 9]
[5]Zhu, Yingguang; Shi, Yian [Organic and Biomolecular Chemistry, 2013, vol. 11, # 43, p. 7451 - 7454]
[6]Location in patent: experimental part Balamurugan, Rengarajan; Naveen, Naganaboina; Manojveer, Seetharaman; Nama, Masthan Vali [Australian Journal of Chemistry, 2011, vol. 64, # 5, p. 567 - 575]
[7]Han, Jun-Fa; Guo, Peng; Chen, Lin; Ye, Ke-Yin [Synthesis, 2022, vol. 54, # 8, p. 1989 - 1995]
[8]Hwang, Soonho; Kang, Hee Ryong; Kim, Sanghee; Haze, Olesya; Danheiser, Rick L. [Organic Syntheses, 2009, vol. 86, p. 225 - 235]

28
[ 1187834-03-2 ]
[ 4039-82-1 ]
[ 1187836-37-8 ]

Yield	Reaction Conditions	Operation in experiment
62%	With N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 50℃; for 14h; Inert atmosphere;	A solution of N-[(2-bromo-1 ,3-thiazol-4-yl)methoxy]-1-(1-methyl-1H-tetrazol-5-yl)-1-phenyl- methanimine (190 mg, 0.50 mmol), benzyl propargyl ether (149 mg, 1.00 mmol), copper(l) iodide (9.5 mg, 0.05 mmol), tetrakis(triphenylphosphine)palladium(0) (28.9 mg, 0.02 mmol), N, N- diisopropylethylamine (258 mg, 2.0 mmol) in degassed tetrahydrofuran (2.5 ml_) was stirred under an Argon atmosphere at 5OºC for 14 h. After the addition of diethylether (2 ml_) the suspension was filtered over a pad of silica gel and the filtrate was concentrated in vacuo. Purification on silica gel afforded N-({2-[3-(benzyloxy)prop-1-yn-1-yl]-1 ,3-thiazol-4-yl}methoxy)-1-(1-methyl-1H-tetrazol-5-yl)-1- phenylmethanimine as a thick oil (144 mg, yield 62% ). HPLC/MS : m/z = 445 (M+H) ; logP(HCooH) = 4.04

Reference： [1]Current Patent Assignee: BAYER AG - WO2009/115557, 2009, A2 Location in patent: Page/Page column 83

29
[ 4039-82-1 ]
[ 16088-62-3 ]
(S)-1-(phenylmethoxy)-2-hexyn-5-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
93%	Stage #1: Benzyl propargyl ether With n-butyllithium In tetrahydrofuran at -78℃; for 0.833333h; Inert atmosphere; Stage #2: With boron trifluoride diethyl etherate In tetrahydrofuran at -78℃; for 0.166667h; Inert atmosphere; Stage #3: (S)-Propylene oxide In tetrahydrofuran at -78℃; for 3h; Inert atmosphere;
78%	Stage #1: Benzyl propargyl ether With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Inert atmosphere; Stage #2: (S)-Propylene oxide With boron trifluoride diethyl etherate In tetrahydrofuran; hexane at -78℃; Inert atmosphere;	(S)-6-(Benzyloxy)hex-4-yn-2-ol ((S)-14). To a stirred solution of 13 (5.350 g, 36.60 mmol) inTHF (240.0 mL) at -78 °C under Ar was added n-BuLi (2.5 M in hexanes, 16.0 mL, 40.0 mmol). After30 min, BF3.Et2O (5.0 mL, 39.90 mmol) was added, followed by (S)-2-methyloxirane ((S)-7) (1.933 g,33.28 mmol). Upon stirring at -78 °C overnight, the reaction was quenched with saturated aqueousNH4Cl, extracted with ethyl acetate, washed with brine, dried over anhydrous Na2SO4, concentrated,and purified by flash chromatography on silica gel (hexanes:ethyl acetate = 10:1) to give (S)-14 as apale yellow oil (5.303 g, 78%). [α]20D = +8.0 (c = 0.2, CHCl3). 1H-NMR (500 MHz, CDCl3)δ 7.36-7.28 (m,5H), 4.59 (s, 2H), 4.18 (d, J = 2.5 Hz, 2H), 3.99-3.93 (m, 1H), 2.48-2.36 (m, 2H), 2.06-1.85 (m, 1H), 1.27 (d,J = 6.0 Hz, 3H); 13C-NMR (125 MHz, CDCl3) δ 137.46, 128.41, 128.03, 127.83, 83.32, 78.51, 71.58, 66.33,57.63, 29.36, 22.35.
78%	Stage #1: Benzyl propargyl ether With n-butyllithium In tetrahydrofuran at -78℃; for 0.5h; Inert atmosphere; Stage #2: (S)-Propylene oxide With boron trifluoride diethyl etherate In tetrahydrofuran at -78℃; for 12h; Inert atmosphere;	2 The synthesis of compound (S)-11 is synthesized as follows Experimental procedure: A 500 mL one-neck round bottom flask was taken, and 9 (5.3 g, 1.0 eq) and dry THF (240 mL) were added, and the mixture was stirred in a -78 ° C cold bath for 15 minutes under Ar atmosphere, and nBuLi (16 mL) was added dropwise. , 1.2 eq), add, and react at -78 ° C for about 30 minutes. BF3·Et2O (5 mL, 1.2 eq) and (S)-propylene oxide (2.3 mL, 1.0 eq) were added dropwise, and the reaction was carried out at -78 ° C for about 12 hours. Work-up: quenched with saturated aqueous sodium bicarbonate and saturated aqueous ammonium chloride. Dry and concentrated with anhydrous sodium sulfate, and the residue was subjected to column chromatography to obtain 5.3 g, yield 78%.

65%

Stage #1: Benzyl propargyl ether With n-butyllithium In tetrahydrofuran; hexane at -78℃; Inert atmosphere; Stage #2: With boron trifluoride diethyl etherate In tetrahydrofuran; hexane at -78℃; for 0.166667h; Inert atmosphere; Stage #3: (S)-Propylene oxide In tetrahydrofuran; hexane at -78℃; for 3h; Inert atmosphere; regioselective reaction;

Reference： [1]Haug, Timm T.; Kirsch, Stefan F. [Organic and Biomolecular Chemistry, 2010, vol. 8, # 5, p. 991 - 993]
[2]Sun, Zhi-Feng; Zhang, Tao; Liu, Jinyang; Du, Zhen-Ting; Zheng, Huaiji [Molecules, 2018, vol. 23, # 3]
[3]Current Patent Assignee: SHAANXI UNIVERSITY OF TECHNOLOGY; NORTHWEST A&F UNIVERSITY - CN108191655, 2018, A Location in patent: Paragraph 0076; 0092; 0114-0116
[4]Location in patent: experimental part Yadav; Raju; Ravindar; Reddy, B.V. Subba [Synthesis, 2010, # 5, p. 797 - 802]

30
[ 4039-82-1 ]
[ 10365-98-7 ]
[ 1300655-61-1 ]

Yield	Reaction Conditions	Operation in experiment
95%	With caesium carbonate; triphenylphosphine; silver(l) oxide In dichloromethane at 35℃; for 3h; Inert atmosphere;	General procedure of Pd nanoparticles catalyzed oxidative cross-coupling reaction To 2 mL of CH2Cl2 were added 1 mmol of arylboronic acid and1.2 mmol of terminal alkyne, then 0.01 mmol of palladium nanoparticles(1 mol%), 0.1 mmol of PPh3 (10 mol%), 1 mmol of Ag2O and 2 mmol of Cs2CO3 were added in turn. The mixture was heated at 35 °C with stirring under a nitrogen atmosphere for the appropriate time (see Table 2, monitored by TLC or GC) till reaction was completed, then centrifuged. The solution was separated and the precipitate was washed with ether (5 mL x 3). The solutions were combined and washed with water, dried over anhydrous Na2SO4 and purified by column chromatography on silica gel with hexaneeethyl acetate (10:1) as eluent to yield the product. The precipitate was further washed sufficiently with methanol and ether, then dried, and the palladium nanoparticles were recovered.

Reference： [1]Location in patent: experimental part Nie, Xiaopeng; Liu, Suli; Zong, Yan; Sun, Peipei; Bao, Jianchun [Journal of Organometallic Chemistry, 2011, vol. 696, # 8, p. 1570 - 1573]

31
[ 4039-82-1 ]
[ 5720-07-0 ]
[ 779355-69-0 ]

Yield	Reaction Conditions	Operation in experiment
84%	With caesium carbonate; triphenylphosphine; silver(l) oxide In dichloromethane at 35℃; for 3h; Inert atmosphere;	General procedure of Pd nanoparticles catalyzed oxidative cross-coupling reaction To 2 mL of CH2Cl2 were added 1 mmol of arylboronic acid and1.2 mmol of terminal alkyne, then 0.01 mmol of palladium nanoparticles(1 mol%), 0.1 mmol of PPh3 (10 mol%), 1 mmol of Ag2O and 2 mmol of Cs2CO3 were added in turn. The mixture was heated at 35 °C with stirring under a nitrogen atmosphere for the appropriate time (see Table 2, monitored by TLC or GC) till reaction was completed, then centrifuged. The solution was separated and the precipitate was washed with ether (5 mL x 3). The solutions were combined and washed with water, dried over anhydrous Na2SO4 and purified by column chromatography on silica gel with hexaneeethyl acetate (10:1) as eluent to yield the product. The precipitate was further washed sufficiently with methanol and ether, then dried, and the palladium nanoparticles were recovered.

Reference： [1]Location in patent: experimental part Nie, Xiaopeng; Liu, Suli; Zong, Yan; Sun, Peipei; Bao, Jianchun [Journal of Organometallic Chemistry, 2011, vol. 696, # 8, p. 1570 - 1573]

32
[ 4039-82-1 ]
[ 87199-17-5 ]
[ 1300655-66-6 ]

Yield	Reaction Conditions	Operation in experiment
87%	With caesium carbonate; triphenylphosphine; silver(l) oxide In dichloromethane at 35℃; for 3h; Inert atmosphere;	General procedure of Pd nanoparticles catalyzed oxidative cross-coupling reaction To 2 mL of CH2Cl2 were added 1 mmol of arylboronic acid and1.2 mmol of terminal alkyne, then 0.01 mmol of palladium nanoparticles(1 mol%), 0.1 mmol of PPh3 (10 mol%), 1 mmol of Ag2O and 2 mmol of Cs2CO3 were added in turn. The mixture was heated at 35 °C with stirring under a nitrogen atmosphere for the appropriate time (see Table 2, monitored by TLC or GC) till reaction was completed, then centrifuged. The solution was separated and the precipitate was washed with ether (5 mL x 3). The solutions were combined and washed with water, dried over anhydrous Na2SO4 and purified by column chromatography on silica gel with hexaneeethyl acetate (10:1) as eluent to yield the product. The precipitate was further washed sufficiently with methanol and ether, then dried, and the palladium nanoparticles were recovered.

Reference： [1]Location in patent: experimental part Nie, Xiaopeng; Liu, Suli; Zong, Yan; Sun, Peipei; Bao, Jianchun [Journal of Organometallic Chemistry, 2011, vol. 696, # 8, p. 1570 - 1573]

33
[ 4039-82-1 ]
[ 511286-63-8 ]
[ 1349191-57-6 ]

Yield	Reaction Conditions	Operation in experiment
96%	Stage #1: Benzyl propargyl ether With n-butyllithium In tetrahydrofuran; N,N,N,N,N,N-hexamethylphosphoric triamide; hexane at -10℃; for 1h; Inert atmosphere; Stage #2: (4S) 3,4-dibenzyl[1,2,3]oxathiazolidine-2,2-dioxide In tetrahydrofuran; N,N,N,N,N,N-hexamethylphosphoric triamide; hexane at -10 - 20℃; Inert atmosphere; regioselective reaction; Further stages;	General procedures for alkylation with cyclic sulfamidates General procedure: Procedure A: To a solution of a terminal alkyne (8.5 mmol, 2 equivalents) in 20 mL freshly distilled THF cooled at -10 °C (salt-ice bath) under argon atmosphere was added n-butyllithium (5.4 mL, 8.6 mmol, 15% solution in hexane) and the solution was stirred at this temperature for 1 h. A solution of a cyclic sulfamidate (4.25 mmol) in 2-3 mL dry THF was then added to the resulting acetylide solution via a syringe. After stirring at -10 °C for 5-6 h, the reaction mixture was allowed to warm up to room temperature gradually with stirring overnight (24 h). The resulting mixture was then treated wih 4 mL 5M HCl solution to hydrolyze the N-sulfate intermediate for 2-3 h before neutralization with saturated NaHCO3 solution. Extraction with ether (three times) and drying over anhydrous Na2SO4 followed by evaporation of volatiles in vacuo gave the crude product. Alkynylated amines were purified by column chromatogarphy using solvent systems (containing 0.5% triethylamine) of different polarity depending on the polarity of the amine product. Procedure B: Using the same stoichiometry and procedure as in A, the reaction was carried out in 20 mL freshly distilled THF containing 2 mL HMPA cooled at -10 °C (ice-salt bath) or at -78 °C (dry ice-acetone bath).

Reference： [1]Eskici, Mustafa; Karanfil, Abdullah; Özer, M. Sabih; Sarikürkcü, Cengiz [Tetrahedron Letters, 2011, vol. 52, # 48, p. 6336 - 6341]

34
[ 4039-82-1 ]
[ 149125-65-5 ]

Yield	Reaction Conditions	Operation in experiment
75%	Stage #1: Benzyl propargyl ether With phenylmagnesium bromide In tetrahydrofuran at 0℃; for 0.166667h; Inert atmosphere; Stage #2: With zinc dibromide In tetrahydrofuran at -78℃; for 0.25h; Inert atmosphere; Further stages;	Typical procedure for the preparation of 1,1-dibromo-1-alkenes General procedure: To a two-neck flask under nitrogen atmosphere and equipped with a magnetic stirring bar, containing 1-alkyne (1.0 mmol) in THF (5.0 mL), a solution of phenyl magnesium bromide (1.1 mL; 1.1 mmol; 1.0 M in THF) was added dropwise at 0 °C. After 10 min, ZnBr2 (0.22 g; 1.1 mmol) in THF (3.0 mL) was added at -78 °C and the mixture was stirred for an additional 15 min. Next, the system was warmed to 25 °C and the THF was totally removed under vacuum and replaced by dry CH2Cl2 (5.0 mL). Then, Cp2Zr(H)Cl (0.26 g; 1.0 mmol) in CH2Cl2 (5.0 mL) was added slowly at 25 °C and the mixture was stirred for 10 min for generation of the 1,1-bismetallic intermediate 5. Finally, the reaction mixture was cooled to 0 °C and NBS (0.44 g, 2.5 mmol) dissolved in THF (5.0 mL) and CH2Cl2 (5.0 mL) was transferred via syringe and the solution stirred for the time needed, as indicated in Table 2. The mixture was diluted with ethyl acetate (50.0 mL) the organic phase was washed with brine (4 × 20.0 mL) and dried over anhydrous magnesium sulfate. After filtration, the solvent was removed under vacuum by rotary evaporation and the crude products were purified by flash chromatography (using silica gel 230-400 mesh and the appropriate mobile phase as shown in Table 1), furnishing the 1,1-dibromo-1-alkenes as a pale yellow oil.

Reference： [1]Location in patent: experimental part Guerrero Jr., Palimécio G.; De Oliveira, Paulo R.; Baroni, Adriano C.M.; Marques, Francisco A.; Labes, Ricardo; Dabdoub, Miguel J. [Tetrahedron Letters, 2012, vol. 53, # 13, p. 1582 - 1586]

35
[ 4039-82-1 ]
1,1-diiodo-3-benzyloxy-1-propene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%	Stage #1: Benzyl propargyl ether With phenylmagnesium bromide In tetrahydrofuran at 0℃; for 0.166667h; Inert atmosphere; Stage #2: With zinc dibromide In tetrahydrofuran at -78℃; for 0.25h; Inert atmosphere; Further stages;	Typical procedure for the preparation of 1,1-diiodo-1-alkenes General procedure: To a two-neck flask under nitrogen atmosphere and equipped with a magnetic stirring bar, containing 1-alkyne (1.0 mmol) in THF (5.0 mL), a solution of phenyl magnesium bromide (1.1 mL; 1.1 mmol; 1.0 M in THF) was added dropwise at 0 °C. After 10 min, ZnBr2 (0.22 g; 1.1 mmol) in THF (3.0 mL) was added at -78 °C and the mixture was stirred for an additional 15 min. Next, the system was warmed to 25 °C and the THF was totally removed under vacuum and replaced by dry CH2Cl2 (5.0 mL). Then, Cp2Zr(H)Cl (0.26 g; 1.0 mmol) in CH2Cl2 (5.0 mL) was added slowly at 25 °C and the mixture was stirred for 10 min for generation of the 1,1-bismetallic intermediate 5. Finally, the reaction mixture was cooled to 0 °C and NBS (0.44 g, 2.5 mmol) dissolved in THF (5.0 mL) and CH2Cl2 (5.0 mL) was transferred via syringe and the solution stirred for the time needed, as indicated in Table 2. The mixture was diluted with ethyl acetate (50.0 mL) the organic phase was washed with brine (4 × 20.0 mL) and dried over anhydrous magnesium sulfate. After filtration, the solvent was removed under vacuum by rotary evaporation and the crude products were purified by flash chromatography (using silica gel 230-400 mesh and the appropriate mobile phase as shown in Table 1), furnishing the 1,1-dibromo-1-alkenes as a pale yellow oil.;The reaction mixture containing the 1,1-bismetallic 5 intermediate was performed as described in the Ref19, and cooled to 0 °C. Then, iodine (0.63 g; 2.5 mmol) dissolved in THF (5.0 mL) was transferred via syringe and the resulting dark-red solution was stirred for the time needed as indicated in Table 2. The resulting solution was transferred to an Erlenmeyer flask and a solution of sodium thiosulfate (5 g/100 mL) was added under stirring until the solution turned pale yellow. The mixture was diluted with ethyl acetate (50.0 mL) and the organic phase was washed with brine (4 × 20.0 mL) and dried over anhydrous magnesium sulfate. After filtration, the solvent was removed under vacuum by rotary evaporation and the crude products were purified by flash chromatography (using silica gel 230-400 mesh and the appropriate mobile phase as shown in Table 1), furnishing the 1,1-diiodo-1-alkenes as a yellow oil.

Reference： [1]Location in patent: experimental part Guerrero Jr., Palimécio G.; De Oliveira, Paulo R.; Baroni, Adriano C.M.; Marques, Francisco A.; Labes, Ricardo; Dabdoub, Miguel J. [Tetrahedron Letters, 2012, vol. 53, # 13, p. 1582 - 1586]

36
[ 4039-82-1 ]
[ 2725-82-8 ]
[ 1409942-12-6 ]

Reference： [1]Journal of Medicinal Chemistry,2012,vol. 55,p. 9669 - 9681

37
[ 50562-79-3 ]
[ 4039-82-1 ]
[ 1438407-99-8 ]

Yield	Reaction Conditions	Operation in experiment
85%	Stage #1: Benzyl propargyl ether With n-butyllithium In tetrahydrofuran at -78℃; for 0.666667h; Inert atmosphere; Stage #2: 1-(4-tolylsulfonyl)indole-3-carboxaldehyde In tetrahydrofuran at -78℃; Inert atmosphere;

Reference： [1]Raji Reddy, Chada; Vijaykumar, Jonnalagadda; Grée, René [Synthesis, 2013, vol. 45, # 6, p. 830 - 836]

38
[ 4039-82-1 ]
[ 2043-61-0 ]
[ 1431291-43-8 ]

Yield	Reaction Conditions	Operation in experiment
63%	With (S)-diphenylprolinol; copper(I) bromide; zinc dibromide In 1,4-dioxane for 13h; Heating; Inert atmosphere; Schlenk technique; enantioselective reaction;
58%	With (S)-diphenylprolinol; zinc dibromide In toluene at 90 - 120℃; for 8.66667h; Schlenk technique; Inert atmosphere; enantioselective reaction;	1 4.2.1 (R)-1-Phenylundeca-1,2-diene (R-4db) General procedure: Typical procedure: To an oven-dried Schlenk tube was added ZnBr2 (229.9 mg, 1.0 mmol, 98% from Alfa) inside a glovebox, the Schlenk tube was then taken out of the glovebox and heated the ZnBr2 until melting under vacuum with a heating gun. (S)-3 (258.4 mg, 1.0 mmol, 98%), 1d (212.1 mg, 1.5 mmol, 98%)/toluene (2 mL), and 2b (212.0 mg, 2.0 mmol)/toluene (1 mL) were then added sequentially under argon atmosphere. The Schlenk tube was then equipped with a condenser and placed in a pre-heated oil bath at 90 °C with stirring for 2.5 h. The reaction mixture was then heated to 120 °C in about 10 min and further stirred for 6 h at 120 °C. After cooling to room temperature, the crude reaction mixture was filtered through a short pad of silica gel and eluented with ether (20 mL). After evaporation, the residue was purified by chromatography on silica gel to afford (R)-4db6 (95.8 mg, 42%).

Reference： [1]Lue, Ruizhi; Ye, Juntao; Cao, Tao; Chen, Bo; Fan, Wu; Lin, Weilong; Liu, Jinxian; Luo, Hongwen; Miao, Bukeyan; Ni, Shengjun; Tang, Xinjun; Wang, Nan; Wang, Yuli; Xie, Xi; Yu, Qiong; Yuan, Weiming; Zhang, Wanli; Zhu, Can; Ma, Shengming [Organic Letters, 2013, vol. 15, # 9, p. 2254 - 2257]
[2]Ye, Juntao; Lü, Ruizhi; Fan, Wu; Ma, Shengming [Tetrahedron, 2013, vol. 69, # 42, p. 8959 - 8963]

39
[ 74213-24-4 ]
[ 4039-82-1 ]
[ 1220521-45-8 ]

Yield	Reaction Conditions	Operation in experiment
91%	With potassium hydrogencarbonate; In 1,2-dimethoxyethane; water; at 0 - 20℃; for 2h;Inert atmosphere;	A solution of <strong>[74213-24-4]dibromoformaldoxime</strong> 7 (20.3 g, 100 mmol) and benzyl propargyl ether 8 (19.0 g, 130 mmol) in DME (200 mL) was cooled to 0 C. A 1.0 M solution of aq. KHCO3 (255 mL, 255 mmol) was added drop wise over 2 h. The resulting yellow solution was allowed to warm to rt overnight. The reaction mixture was diluted with water (200 mL) and extracted with EtOAc (3 x 400 mL). The combined organic extracts were dried over MgSO4, filtered, and concentrated under reduced pressure. The resulting yellow oil was purified by column chromatography (SiO2, 10:1 hexanes/EtOAc) to afford 9 (25.2 g, 94.1 mmol, 91%) as a colorless oil.

Reference： [1]Tetrahedron Letters,2013,vol. 54,p. 2645 - 2647

40
[ 3240-34-4 ]
[ 4039-82-1 ]
[ 87385-73-7 ]

Yield	Reaction Conditions	Operation in experiment
87%	With silver(I) acetate In acetonitrile at 25℃; for 14h;	3.2. General procedure for preparation of α-acetoxy ketones 3 starting from terminal alkynes 1 General procedure: To a mixture of PhI(OAc)2 (1 mmol, 322 mg) and CH3COOAg (0.1 mmol, 17 mg) in CH3CN (10 ml) was added alkyne (1 mmol).The mixture was stirred at room temperature. When PhI(OAc)2 was completely disappeared by TLC analysis, the mixture was concentrated in vacuum. The residue was purified by column chromatography on silica gel with EtOAc/petroleum ether 6:1 as eluent.

Reference： [1]Deng, Guisheng; Luo, Jing [Tetrahedron, 2013, vol. 69, # 29, p. 5937 - 5944]

41
[ 67-56-1 ]
[ 4039-82-1 ]
[ 4126-60-7 ]

Reference： [1]Angewandte Chemie - International Edition,2013,vol. 52,p. 10023 - 10026
Angew. Chem.,2013,vol. 125,p. 10207 - 10210,4

42
[ 2439-85-2 ]
[ 4039-82-1 ]
[ 1561176-69-9 ]

Reference： [1]Chemical Communications,2014,vol. 50,p. 2360 - 2363

43
[ 4039-82-1 ]
[ 672339-38-7 ]
[ 1430717-61-5 ]

Yield	Reaction Conditions	Operation in experiment
84%	Stage #1: (Z)-2,3,3,3-tetrafluoro-1-iodoprop-1-ene With palladium diacetate; triphenylphosphine In N,N-dimethyl-formamide at 25℃; for 0.333333h; Inert atmosphere; Stage #2: Benzyl propargyl ether With copper(l) iodide; triethylamine In N,N-dimethyl-formamide at 25℃; for 24h; Inert atmosphere;	4.3 Typical procedure for the preparation of CF₃-containing enynes General procedure: To a solution of Pd(OAc)2 (224mg, 1.0mmol) in DMF (133mL) was added triphenyl phosphine (525mg, 2.0mmol) at 25°C. After the mixture was stirred for 20min, 3,3,3,4-tetrafluoro-1-iodo-1-propene (4.80g, 20mmol) was added into the reaction mixture, then stirred for 20min. After that, ethynylbenzene (4.18g, 24mmol), triethylamine (4.2mL, 3.07g, 30mmol), and copper iodide (381mg, 2mmol) was added in this order into the above mixture. The whole was stirred for 24h, then quenched with satd NH4Cl aq. The mixture was extracted with ether three time, and the combined organic layers were dried over anhydrous Na2SO4, then filtered. The filtrate was evaporated to give the corresponding crude materials, which was purified by silica gel column chromatography, affording the 1,1,1,2-tetrafluoro-5-phenyl-2-penten-4-yne (2e) (5.38g, 18.8mmol, 94% yield). Compounds 2a-d was known compounds, which was reported in the previous publication.5a,6a

Reference： [1]Konno, Tsutomu; Kishi, Misato; Ishihara, Takashi; Yamada, Shigeyuki [Tetrahedron, 2014, vol. 70, # 14, p. 2455 - 2463]

44
[ 4039-82-1 ]
[ 352-11-4 ]
[ 1573119-06-8 ]

Yield	Reaction Conditions	Operation in experiment
73%	With sodium azide; 1,10-Phenanthroline; copper(II) acetate monohydrate; sodium L-ascorbate In ethanol; water at 20℃; for 36h;	Typical Procedure for the Synthesis of Triazoles Derived from Benzyl Alcohol General procedure: To a 20-mL, round-bottomed flask equipped with a magnetic stirrer were charged 7mg (0.035 mmol, 5 mol%) of Cu(OAc)2 H2O, 7mg (0.035 mmol,5 mol%) of 1,10-phenanthroline monohydrate, and 139 mg (0.70 mmol) of sodium L-ascorbate. After addition of 5mL of a mixture of EtOH-H2O (4:1 v=v), the resulting suspension was stirred for 5 min at room temperature. Subsequently, 103 mg(0.70 mmol) of I, 50mg (0.77 mmol) of sodium azide, and 0.09mL (0.83 mmol) of benzylchloride were added to the reaction mixture, which was stirred for 36 h at room temperature. Then 5mL of H2O were added to the reaction mixture, and the precipitate was filtered off, washed thoroughly with H2O and petroleum ether, and dried under vacuum. The crude product was purified by column chromatography (CH2Cl2-MeOH 98:2 v=v) to afford 150 mg (77% yield) of 1a as a white solid.

Reference： [1]Mendoza-Espinosa, Daniel; Negron-Silva, Guillermo; Lomas-Romero, Leticia; Gutierrez-Carrillo, Atilano; Santillan, Rosa [Synthetic Communications, 2014, vol. 44, # 6, p. 807 - 817]

45
[ 4039-82-1 ]
[ 104-83-6 ]
[ 1573119-07-9 ]

Yield	Reaction Conditions	Operation in experiment
73%	With sodium azide; 1,10-Phenanthroline; copper(II) acetate monohydrate; sodium L-ascorbate In ethanol; water at 20℃; for 36h;	Typical Procedure for the Synthesis of Triazoles Derived from Benzyl Alcohol General procedure: To a 20-mL, round-bottomed flask equipped with a magnetic stirrer were charged 7mg (0.035 mmol, 5 mol%) of Cu(OAc)2 H2O, 7mg (0.035 mmol,5 mol%) of 1,10-phenanthroline monohydrate, and 139 mg (0.70 mmol) of sodium L-ascorbate. After addition of 5mL of a mixture of EtOH-H2O (4:1 v=v), the resulting suspension was stirred for 5 min at room temperature. Subsequently, 103 mg(0.70 mmol) of I, 50mg (0.77 mmol) of sodium azide, and 0.09mL (0.83 mmol) of benzylchloride were added to the reaction mixture, which was stirred for 36 h at room temperature. Then 5mL of H2O were added to the reaction mixture, and the precipitate was filtered off, washed thoroughly with H2O and petroleum ether, and dried under vacuum. The crude product was purified by column chromatography (CH2Cl2-MeOH 98:2 v=v) to afford 150 mg (77% yield) of 1a as a white solid.

Reference： [1]Mendoza-Espinosa, Daniel; Negron-Silva, Guillermo; Lomas-Romero, Leticia; Gutierrez-Carrillo, Atilano; Santillan, Rosa [Synthetic Communications, 2014, vol. 44, # 6, p. 807 - 817]

46
[ 4039-82-1 ]
[ 589-15-1 ]
[ 1573119-08-0 ]

Yield	Reaction Conditions	Operation in experiment
85%	With sodium azide; 1,10-Phenanthroline; copper(II) acetate monohydrate; sodium L-ascorbate In ethanol; water at 20℃; for 36h;	Typical Procedure for the Synthesis of Triazoles Derived from Benzyl Alcohol General procedure: To a 20-mL, round-bottomed flask equipped with a magnetic stirrer were charged 7mg (0.035 mmol, 5 mol%) of Cu(OAc)2 H2O, 7mg (0.035 mmol,5 mol%) of 1,10-phenanthroline monohydrate, and 139 mg (0.70 mmol) of sodium L-ascorbate. After addition of 5mL of a mixture of EtOH-H2O (4:1 v=v), the resulting suspension was stirred for 5 min at room temperature. Subsequently, 103 mg(0.70 mmol) of I, 50mg (0.77 mmol) of sodium azide, and 0.09mL (0.83 mmol) of benzylchloride were added to the reaction mixture, which was stirred for 36 h at room temperature. Then 5mL of H2O were added to the reaction mixture, and the precipitate was filtered off, washed thoroughly with H2O and petroleum ether, and dried under vacuum. The crude product was purified by column chromatography (CH2Cl2-MeOH 98:2 v=v) to afford 150 mg (77% yield) of 1a as a white solid.

Reference： [1]Mendoza-Espinosa, Daniel; Negron-Silva, Guillermo; Lomas-Romero, Leticia; Gutierrez-Carrillo, Atilano; Santillan, Rosa [Synthetic Communications, 2014, vol. 44, # 6, p. 807 - 817]

47
[ 4039-82-1 ]
[ 16004-15-2 ]
[ 1573119-09-1 ]

Yield	Reaction Conditions	Operation in experiment
79%	With sodium azide; 1,10-Phenanthroline; copper(II) acetate monohydrate; sodium L-ascorbate In ethanol; water at 20℃; for 36h;	Typical Procedure for the Synthesis of Triazoles Derived from Benzyl Alcohol General procedure: To a 20-mL, round-bottomed flask equipped with a magnetic stirrer were charged 7mg (0.035 mmol, 5 mol%) of Cu(OAc)2 H2O, 7mg (0.035 mmol,5 mol%) of 1,10-phenanthroline monohydrate, and 139 mg (0.70 mmol) of sodium L-ascorbate. After addition of 5mL of a mixture of EtOH-H2O (4:1 v=v), the resulting suspension was stirred for 5 min at room temperature. Subsequently, 103 mg(0.70 mmol) of I, 50mg (0.77 mmol) of sodium azide, and 0.09mL (0.83 mmol) of benzylchloride were added to the reaction mixture, which was stirred for 36 h at room temperature. Then 5mL of H2O were added to the reaction mixture, and the precipitate was filtered off, washed thoroughly with H2O and petroleum ether, and dried under vacuum. The crude product was purified by column chromatography (CH2Cl2-MeOH 98:2 v=v) to afford 150 mg (77% yield) of 1a as a white solid.

Reference： [1]Mendoza-Espinosa, Daniel; Negron-Silva, Guillermo; Lomas-Romero, Leticia; Gutierrez-Carrillo, Atilano; Santillan, Rosa [Synthetic Communications, 2014, vol. 44, # 6, p. 807 - 817]

48
[ 4039-82-1 ]
1,8-bis(azidomethyl)naphthalene [ No CAS ]
C₂₆H₂₄N₆O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
84.1%	With copper(ll) sulfate pentahydrate; sodium L-ascorbate In N,N-dimethyl-formamide at 20℃; for 2h; Inert atmosphere;	2.6. Synthesis of compound 2 Under nitrogen, 3 (119 mg, 0.5 mmol), 5 (220 mg, 1.5 mmol), CuSO45H2O (0.1 mmol, 25 mg, 0.2 eq) and sodium ascorbate (0.15 mmol, 30 mg, 0.3 eq) were added into 5 mL DMF. The mixture was stirred at room temperature for 2 h, and then diluted with ethyl acetate (40 mL) and washed with water (3 30 mL). The organic phase was dried over MgSO4, filtered, and the solven twas removed under reduced pressure. The crude product was purified by column chromatography (SiO2, CH2Cl2/MeOH = 95/5), yielding 2 as a white powder (0.285 g, 84.1%). 1H NMR (400 MHz, CDCl3): d (ppm) = 8.02 (d, J = 7.5 Hz, 2H), 7.60-7.51 (m, 2H), 7.45 (d, J = 6.7 Hz, 2H), 7.34 (m, 12H), 6.10 (s, 4H), 4.66 (s, 4H), 4.60 (s, 4H). 13C NMR (100 MHz, CDCl3): d (ppm) = 145.6, 137.6, 136.3, 132.6, 132.0, 130.0, 129.5, 128.4, 127.9, 127.8, 125.8, 122.6, 72.7, 63.7, 55.1. ESI-TOF-MS: 531.2975 (M + 1).

Reference： [1]Dai, Bo-Na; Cao, Qian-Yong; Wang, Ling; Wang, Zi-Chen; Yang, Zhenyu [Inorganica Chimica Acta, 2014, vol. 423, # PART A, p. 163 - 167]

49
[ 4039-82-1 ]
[ 79629-41-7 ]

Yield	Reaction Conditions	Operation in experiment
71%	With 1,1-dibromomethane In <i>N</i>,<i>N</i>-dimethyl-aniline at 120℃; for 12h; Inert atmosphere; Schlenk technique;	2. General procedure General procedure: Terminal alkynes(0.5 mmol), dibromomethane (2.5 mmol), N,N-dimethylaniline (1.5 mmol) wereplaced in a Schlenk tube (10 mL), and the mixture was stirred at 120 °C for 12 h. Then, the mixture was cooledto room temperature, washed with saturated Na2CO3solution. The crude product was extracted with ethyl acetate three times. Theorganic layer was dried over anhydrous Na2SO4, andconcentrated under reduced pressure. The residue was purified by columnchromatography on silica gel and eluted with petroleum to afford the analyticallypure products.

Reference： [1]Chen, Xiuling; Chen, Tieqiao; Xiang, Yuqiang; Zhou, Yongbo; Han, Daoqing; Han, Li-Biao; Yin, Shuang-Feng [Tetrahedron Letters, 2014, vol. 55, # 33, p. 4572 - 4575]

50
[ 4039-82-1 ]
1,8-bis(azidomethyl)naphthalene [ No CAS ]
C₃₂H₃₀N₆O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
84.1%	With sodium 2-(1,2-dihydroxyethyl)-4-hydroxy-5-oxo-2,5-dihydro-furan-3-olate; copper(II) sulfate In N,N-dimethyl-formamide at 20℃; for 2h; Inert atmosphere;	Synthesis of compound 2 Under nitrogen, 3 (119 mg, 0.5 mmol), 5 (220 mg, 1.5 mmol),CuSO45H2O (0.1 mmol, 25 mg, 0.2 eq) and sodium ascorbate(0.15 mmol, 30 mg, 0.3 eq) were added into 5 mL DMF. The mixturewas stirred at room temperature for 2 h, and then diluted withethyl acetate (40 mL) and washed with water (3 30 mL). Theorganic phase was dried over MgSO4, filtered, and the solventwas removed under reduced pressure. The crude product was purifiedby column chromatography (SiO2, CH2Cl2/MeOH = 95/5),yielding 2 as a white powder (0.285 g, 84.1%). 1H NMR (400 MHz,CDCl3): d (ppm) = 8.02 (d, J = 7.5 Hz, 2H), 7.60-7.51 (m, 2H), 7.45(d, J = 6.7 Hz, 2H), 7.34 (m, 12H), 6.10 (s, 4H), 4.66 (s, 4H), 4.60(s, 4H). 13C NMR (100 MHz, CDCl3): d (ppm) = 145.6, 137.6, 136.3,132.6, 132.0, 130.0, 129.5, 128.4, 127.9, 127.8, 125.8, 122.6, 72.7,63.7, 55.1. ESI-TOF-MS: 531.2975 (M + 1).
84.1%	With copper(ll) sulfate pentahydrate; sodium L-ascorbate In N,N-dimethyl-formamide at 20℃; for 2h; Inert atmosphere;	2.6. Synthesis of compound 2 Under nitrogen, 3 (119 mg, 0.5 mmol), 5 (220 mg, 1.5 mmol),CuSO4.5H2O (0.1 mmol, 25 mg, 0.2 eq) and sodium ascorbate(0.15 mmol, 30 mg, 0.3 eq) were added into 5 mL DMF. The mixture was stirred at room temperature for 2 h, and then diluted with ethyl acetate (40 mL) and washed with water (3 30 mL). The organic phase was dried over MgSO4, filtered, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography (SiO2, CH2Cl2/MeOH = 95/5),yielding 2 as a white powder (0.285 g, 84.1%). 1H NMR (400 MHz,CDCl3): d (ppm) = 8.02 (d, J = 7.5 Hz, 2H), 7.60-7.51 (m, 2H), 7.45(d, J = 6.7 Hz, 2H), 7.34 (m, 12H), 6.10 (s, 4H), 4.66 (s, 4H), 4.60(s, 4H). 13C NMR (100 MHz, CDCl3): d (ppm) = 145.6, 137.6, 136.3,132.6, 132.0, 130.0, 129.5, 128.4, 127.9, 127.8, 125.8, 122.6, 72.7,63.7, 55.1. ESI-TOF-MS: 531.2975 (M + 1).

Reference： [1]Dai, Bo-Na; Cao, Qian-Yong; Wang, Ling; Wang, Zi-Chen; Yang, Zhenyu [Inorganica Chimica Acta, 2014, vol. 423, # 1, p. 163 - 167]
[2]Dai, Bo-Na; Cao, Qian-Yong; Wang, Ling; Wang, Zi-Chen; Yang, Zhenyu [Inorganica Chimica Acta, 2014, # PA, p. 163 - 167]

51
[ 92-43-3 ]
[ 4039-82-1 ]
3-(2-(benzyloxymethyl)-1H-indol-1-yl)propanamide [ No CAS ]

Reference： [1]Organic Letters,2014,vol. 16,p. 5976 - 5979

52
[ 1214264-88-6 ]
[ 4039-82-1 ]
[ 1067-52-3 ]
(E)-2-(3-(benzyloxy)-1-(tributylstannyl)prop-1-en-2-yl)-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinine [ No CAS ]

Reference： [1]Chemical Communications,2015,vol. 51,p. 6297 - 6300

53
[ 519003-01-1 ]
[ 4039-82-1 ]
(R)-5-((4-((benzyloxy)methyl)-1H-1,2,3-triazol-1-yl)methyl)-3-(3-fluoro-4-iodophenyl)oxazolidin-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
93%	With copper(II) sulfate; sodium L-ascorbate In water; <i>tert</i>-butyl alcohol at 20℃; for 1h;	9.1 (R)-5-((4-((benzyloxy)methyl)-1H-1,2,3-triazol-1-yl)methyl)-3-(3-fluoro-4-iodophenyl)oxazolidin-2-one The subject compound (66 mg, 93%) was obtained from (R)-5-(Azidomethyl)-3-(3-fluoro-4-iodophenyl)oxazolidin-2-one (50 mg, 0.14 mmol) and ((prop-2-yn-1-yloxy)methyl)benzene (41 mg, 0.28 mmol). 1H NMR (DMSO, 400 MHz): δ 8.20 (s, 1H), δ7.80 (t, J=8.0 Hz, 1H), 7.51 (dd, 1H), 7.35 (m, 5H), 7.15 (dd, 1H), 5.17 (m, 1H), 4.84 (d, 1H), 4.58 (s, 1H), 4.49 (s, 1H), 4.25 (t, 1H), 3.92 (dd, 1H).

Reference： [1]Current Patent Assignee: POHANG UNIVERSITY OF SCIENCE AND TECHNOLOGY; KOREA INSTITUTE OF SCIENCE AND TECHNOLOGY - US2015/148386, 2015, A1 Location in patent: Paragraph 0246; 0247; 0248

54
[ 14593-43-2 ]
[ 4039-82-1 ]

Yield	Reaction Conditions	Operation in experiment
96%	Stage #1: benzyl allyl ether With pyridinium perbromide hydrobromide In acetonitrile at 20℃; for 12h; Molecular sieve; Inert atmosphere; Stage #2: With tetra(n-butyl)ammonium hydroxide; dimethyl sulfoxide; triethylamine In water; acetonitrile at 0 - 60℃; for 2h; Molecular sieve; Inert atmosphere;	One-Pot Synthesis of 4 by Method B; General Procedure General procedure: A mixture of allyl alcohol derivative 1 (x g, 1.0 equiv), py·HBr3 (1.1equiv), and MS 13X (ca. 10x g) in MeCN (y mL, 0.1 M) was stirred at r.t. for 12-14 h. Then, DMSO (7y mL), TBAOH (3.1 equiv, 40% in H2O),and Et3N (1.1 equiv) were added to the reaction mixture at 0 °C and the system was heated to 60 °C. The reaction was quenched with sat.aq NH4Cl at 0 °C. After the removal of MS 13X through a cotton filter, the resulting filtrate was extracted with hexane-EtOAc (2:1, 3 × 30mL) and dried (MgSO4). The combined extracts were concentrated under reduced pressure, and the residue was purified by column chromatography (silica gel) to afford the propargyl alcohol derivative 4.

Reference： [1]Kutsumura, Noriki; Inagaki, Mai; Kiriseko, Akito; Saito, Takao [Synthesis, 2015, vol. 47, # 13, p. 1844 - 1850]

55
[ 497-25-6 ]
[ 4039-82-1 ]
[ 1274906-21-6 ]

Yield	Reaction Conditions	Operation in experiment
89%	With pyridine; oxygen; caesium carbonate; copper dichloride In toluene at 70℃; for 12h; Molecular sieve;	4.3. General procedure for ynamides synthesis General procedure: In a two-neck round-bottom flask equipped with a stir-bar, CuCl2 (0.2 equiv), oxazolidin-2-one (5.0 equiv), Na2CO3 or Cs2CO3 (2.0 equiv) and molecular sieve (4) were combined. The reaction flask was purged with oxygen for 15 min. A solution of pyridine (2.0 equiv) in dry toluene (0.2 M) was added to the reaction flask via a syringe at room temperature. Two balloons filled with oxygen were connected to the reaction flask via a needle. The flask was placed in an oil-bath and heated to 70 °C. A solution of alkyne (1.0 equiv) in dry toluene was added over 4 h using a syringe pump. After the addition was completed, the reaction mixture was stirred at 70 °C for 8 h and then cooled to room temperature. The crude mixture was concentrated under vacuum and the residue was purified by flash chromatography on silica gel.
	With pyridine; oxygen; sodium carbonate; copper dichloride In toluene at 70℃; for 8h;
	Stage #1: dimethylenecyclourethane With pyridine; sodium carbonate; copper dichloride In toluene at 70℃; for 0.5h; Stage #2: Benzyl propargyl ether In toluene at 70℃;	General procedure of synthesis of ynamides General procedure: In a 250 cm3 two-neck round-bottom flask equipped with astir-bar, CuCl2(0.2 equiv.), nitrogen nucleophile (5 equiv.),and Na2CO3(2 equiv.) were combined. The reaction flask was purged with oxygen gas. A solution of pyridine(2 equiv.) in dry toluene (0.06 M) was added to the reactionflask and stirred at 70 °C. After 0.5 h, a solution ofthe respective alkyne (1.0 equiv.) in dry toluene (0.033 M)was added to the flask over 4 h using a syringe pump. Afteraddition of alkyne/toluene solution, the reaction mixture wasallowed to stir at 70 °C overnight. After cooling to r.t., thecrude mixture was concentrated under reduced pressure. Theresidue was purified by column chromatography on silicagel.

Reference： [1]Lingua, Hugo; Vibert, François; Mouysset, Dominique; Siri, Didier; Bertrand, Michèle P.; Feray, Laurence [Tetrahedron, 2017, vol. 73, # 25, p. 3415 - 3422]
[2]Dwivedi, Vikas; Hari Babu, Madala; Kant, Ruchir; Sridhar Reddy, Maddi [Chemical Communications, 2015, vol. 51, # 81, p. 14996 - 14999]
[3]Brutiu, Bogdan R.; Bubeneck, Wilhelm Andrei; Cvetkovic, Olivera; Li, Jing; Maulide, Nuno [Monatshefte fur Chemie, 2019, vol. 150, # 1, p. 3 - 10]

56
[ 4039-82-1 ]
3-azido-5-chloro-2-hydroxybenzoic acid [ No CAS ]
5-chloro-2-hydroxy-3-[4-(benzyloxymethyl)-1H-1,2,3-triazol-1-yl]benzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With copper(ll) sulfate pentahydrate; sodium L-ascorbate In water; <i>tert</i>-butyl alcohol at 20℃;	The general procedure for the synthesis of 5-chloro-2-hydroxy-3-triazolylbenzoic acids (5) General procedure: In a 250-mL three-necked round-bottom flask was added20 mL of tert-butanol/water (V:V = 1:1) mixed solutioncontaining 3-azido-5-chloro-2-hydroxybenzoic acid(427 mg, 2 mmol) and terminal alkyne (2.2 mmol). To thissolution were then added sodium ascorbate (200 mg,1 mmol, 50 % equiv.) and CuSO45H2O (50 mg,0.2 mmol, 10 % equiv.). The reaction mixture was stirredfor about 8-12 h at room temperature. The precipitate wasfiltered, washed with water and then petroleum ether, anddried under vacuum to give gray solid.

Reference： [1]Chen, Jie; Liu, Cheng-Fu; Yang, Cheng-Wen; Zeng, Cheng-Chu; Liu, Wei; Hu, Li-Ming [Medicinal Chemistry Research, 2015, vol. 24, # 7, p. 2950 - 2959]

57
[ 4039-82-1 ]
[ 116026-98-3 ]
tert-butyl 2-((benzyloxy)methyl)-1H-pyrrolo[3,2-b]pyridine-1-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
91%	With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In N,N-dimethyl-formamide; at 20℃; for 43h;Inert atmosphere; Sealed tube;	A resealable pressure vessel was charged with tert-butyl (2-bromopyridin-3- yl) carbamate (6.75 g, 24.7 mmol), ((prop-2-yn-l-yloxy)methyl)benzene (4.34 g, 29.7 mmol), bis(triphenylphosphine) palladium(II) chloride (0.87g, 1.24 mmol), copper(I) iodide (0.47 g, 2.47 mmol), triethylamine (69 mL, 494 mmol) and DMF (25 mL). The mixture was degassed by bubbling nitrogen through for several minutes, the flask was sealed and the reaction mixture was stirred overnight. After ~18h, LC/MS showed a -7:4 mixture of intermediate and fully cyclized product. This ratio was essentially unchanged after an additional ~7h, so an additional portion of copper(I) iodide (lg, ~5 mmol) was added and the mixture was stirred at rt for an additional ~18h, at which time, the conversion was complete by LC/MS (LC/MS Method A: retention time = 3.41min, M+H = 339.15). The mixture was diluted with EtOAc and washed with saturated ammonium chloride (4x) and brine (lx). The organics were dried over sodium sulfate, filtered and evaporated, and the crude material purified by silica gel chromatography, eluting with 20-50% EtOAc in hexanes, affording tert-butyl 2-((benzyloxy)methyl)-lH-pyrrolo[3,2-b]pyridine-l- carboxylate (7.6 g, 91%). 1H NMR (400MHz, CHLOROFORM-d) δ = 8.52 (d, J=3.5 Hz, 1H), 8.34 (d, J=8.3 Hz, 1H), 7.48 - 7.32 (m, 5H), 7.21 (dd, J=4.6, 8.4 Hz, 1H), 6.95 (s, 1H), 4.97 (d, J=0.8 Hz, 2H), 4.72 (s, 2H), 1.69 (s, 9H).
	With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In N,N-dimethyl-formamide;Sealed tube;	A resealable pressure vessel was charged with tert-butyl (2-bromopyridin-3-yl) carbamate 30 (6.75 g, 24.7 mmol), ((prop-2-yn-1-yloxy)methyl)benzene 12 (4.34 g, 29.7 mmol), bis(triphenylphosphine) palladium(II) chloride (0.87g, 1.24 mmol), copper(I) iodide (0.47 g, 2.47 mmol), triethylamine (69 mL, 494 mmol) and DMF (25 mL). The mixture was degassed by bubbling nitrogen through for several minutes, the flask was sealed and the reaction mixture was stirred overnight. After ~18h, LC/MS showed a ~7:4 mixture of intermediate and fully cyclized product. This ratio was essentially unchanged after an additional ~7h, so an additional portion of copper(I) iodide (1g, ~5 mmol) was added and the mixture was stirred at rt for an additional ~18h, at which time, the conversion was complete by LC/MS (LC/MS Method A: retention time = 3.41min, M+H = 339.15). The mixture was diluted with EtOAc and washed with saturated ammonium chloride (4x) and brine (1x). The organics were dried over sodium sulfate, filtered and evaporated, and the crude material purified by silica gel chromatography, eluting with 20-50% EtOAc in hexanes, affording tert-butyl 2-((benzyloxy)methyl)-1H-pyrrolo[3,2-b]pyridine-1-carboxylate (7.6 g, 91%). 1H NMR (400MHz, CHLOROFORM-d) δ = 8.52 (d, J=3.5 Hz, 1H), 8.34 (d, J=8.3 Hz, 1H), 7.48 - 7.32 (m, 5H), 7.21 (dd, J=4.6, 8.4 Hz, 1H), 6.95 (s, 1H), 4.97 (d, J=0.8 Hz, 2H), 4.72 (s, 2H), 1.69 (s, 9H).

Reference： [1]Patent: WO2015/191401,2015,A1 .Location in patent: Page/Page column 107-108
[2]Tetrahedron Letters,2018,vol. 59,p. 751 - 754

58
[ 4039-82-1 ]
[ 154048-89-2 ]
tert-butyl 2-((benzyloxy)methyl)-1H-pyrrolo[2,3-c]pyridine-1-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In N,N-dimethyl-formamide; at 80℃; for 4h;Inert atmosphere; Sealed tube;	Alternate Preparation: Tert-butyl 2-((benzyloxy)methyl)-lH-pyrrolo[2,3- c]pyridine-l-carboxylate was also prepared in an alternate preparation directly from tert-butyl <strong>[154048-89-2]tert-butyl (4-iodopyridin-3-yl)carbamate</strong>: In a sealed tube was added ((prop-2-yn-l-yloxy)methyl)benzene (104 mu, 0.750 mmol) and tert-butyl (4- iodopyridin-3-yl)carbamate (200 mg, 0.625 mmol) in DMF (625 mu). To this was added PdCl2(PPh3)2 (21.93 mg, 0.031 mmol), copper(I) iodide (11.90 mg, 0.062 mmol) and TEA (1742 mu, 12.50 mmol). This reaction was then degassed for 15 minutes and then allowed to stir at 80 C sealed. After 4 hours the reaction was complete. The reaction mixture was poured into ethyl acetate and saturated ammonium chloride. The organic was collected and washed several times with ammonium chloride. The organic was then purified on the biotage eluting in 10% ethyl acetate for 10 column volumes and then 10%-40% Ethyl acetate in hexanes over 10 column volumes. The product, tert-butyl 2-((benzyloxy)methyl)-lH- pyrrolo[2,3-c]pyridine-l-carboxylate (179 mg, 85% yield) was collected as a dark yellow oil. 1H NMR (400MHz, CHLOROFORM-d) delta = 9.58 - 9.20 (m, 1H), 8.70 - 8.42 (m, 1H), 7.54 - 7.34 (m, 6H), 6.78 (s, 1H), 4.98 (d, J=1.3 Hz, 2H), 4.73 (s, 2H), 1.69 (s, 9H).
85%	With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In N,N-dimethyl-formamide; at 80℃; for 4h;Sealed tube;	Tert-butyl 2-((benzyloxy)methyl)-1H-pyrrolo[2,3-c]pyridine-1-carboxylate was also prepared in an alternate preparation directly from tert-butyl <strong>[154048-89-2]tert-butyl (4-iodopyridin-3-yl)carbamate</strong>: In a sealed tube was added ((prop-2-yn-1-yloxy)methyl)benzene 12 (104 mul, 0.750 mmol) and <strong>[154048-89-2]tert-butyl (4-iodopyridin-3-yl)carbamate</strong> 10 (200 mg, 0.625 mmol) in DMF (625 mul). To this was added PdCl2(PPh3)2 (21.93 mg, 0.031 mmol), copper(I) iodide (11.90 mg, 0.062 mmol) and TEA (1742 mul, 12.50 mmol). This reaction was then degassed for 15 minutes and then allowed to stir at 80 C sealed. After 4 hours the reaction was complete. The reaction mixture was poured into ethyl acetate and saturated ammonium chloride. The organic was collected and washed several times with ammonium chloride. The organic was then purified on the biotage eluting in 10% ethyl acetate for 10 column volumes and then 10%-40% Ethyl acetate in hexanes over 10 column volumes. The product, tert-butyl 2-((benzyloxy)methyl)-1H-pyrrolo[2,3-c]pyridine-1-carboxylate (179 mg, 85% yield) was collected as a dark yellow oil. 1H NMR (400MHz, CHLOROFORM-d) delta = 9.58 - 9.20 (m, 1H), 8.70 - 8.42 (m, 1H), 7.54 - 7.34 (m, 6H), 6.78 (s, 1H), 4.98 (d, J=1.3 Hz, 2H), 4.73 (s, 2H), 1.69 (s, 9H).

Reference： [1]Patent: WO2015/191401,2015,A1 .Location in patent: Page/Page column 30-31
[2]Tetrahedron Letters,2018,vol. 59,p. 751 - 754

59
[ 4039-82-1 ]
[ 154048-89-2 ]
tert-butyl (4-(3-(benzyloxy)prop-1-yn-1-yl)pyridin-3-yl)carbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
98%	With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In N,N-dimethyl-formamide; for 7h;Inert atmosphere; Sealed tube;	A resealable pressure vessel was charged with tert-butyl tert-butyl (4- iodopyridin-3-yl)carbamate (1.54 g, 4.8 mmol), ((prop-2-yn-l-yloxy)methyl)benzene (0.84 g, 5.8 mmol), bis(triphenylphosphine) palladium(II) chloride (0.17g, 0.24 mmol), copper(I) iodide (0.09 g, 0.48mmol), triethylamine (15 mL, 108 mmol) and DMF (5 mL). The mixture was degassed by bubbling nitrogen through for several minutes, the flask was sealed and the reaction mixture was stirred for 7h. The mixture was diluted with EtO Ac and washed with saturated ammonium chloride (2x) and brine (lx). The organics were dried over sodium sulfate, filtered and evaporated, and the crude material purified by silica gel chromatography, eluting with 12-100% EtO Ac in hexanes, affording tert-butyl (4-(3-(benzyloxy)prop- 1 -yn- 1 -yl)pyridin-3- yl)carbamate (1.6 g, 98%). 1H NMR (400MHz, CHLOROFORM-d) delta = 9.44 (s, 1H), 8.28 (d, J=4.8 Hz, 1H), 7.45 - 7.33 (m, 5H), 7.26 (d, J=4.8 Hz, 1H), 7.14 - 6.93 (m, 1H), 4.71 (s, 2H), 4.50 (s, 2H), 1.56 (s, 9H).
	With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In N,N-dimethyl-formamide; at 20℃;Sealed tube;	A resealable pressure vessel was charged with tert-butyl <strong>[154048-89-2]tert-butyl (4-iodopyridin-3-yl)carbamate</strong> (1.54 g, 4.8 mmol), ((prop-2-yn-1-yloxy)methyl)benzene (0.84 g, 5.8 mmol), bis(triphenylphosphine) palladium(II) chloride (0.17g, 0.24 mmol), copper(I) iodide (0.09 g, 0.48mmol), triethylamine (15 mL, 108 mmol) and DMF (5 mL). The mixture was degassed by bubbling nitrogen through for several minutes, the flask was sealed and the reaction mixture was stirred for 7h.. The mixture was diluted with EtOAc and washed with saturated ammonium chloride (2x) and brine (1x). The organics were dried over sodium sulfate, filtered and evaporated, and the crude material purified by silica gel chromatography, eluting with 12-100% EtOAc in hexanes, affording tert-butyl (4-(3-(benzyloxy)prop-1-yn-1-yl)pyridin-3-yl)carbamate (1.6 g, 98%). 1H NMR (400MHz, CHLOROFORM-d) delta = 9.44 (s, 1H), 8.28 (d, J=4.8 Hz, 1H), 7.45 - 7.33 (m, 5H), 7.26 (d, J=4.8 Hz, 1H), 7.14 - 6.93 (m, 1H), 4.71 (s, 2H), 4.50 (s, 2H), 1.56 (s, 9H).

Reference： [1]Patent: WO2015/191401,2015,A1 .Location in patent: Page/Page column 28-29
[2]Tetrahedron Letters,2018,vol. 59,p. 751 - 754

60
[ 4039-82-1 ]
[ 211029-67-3 ]
tert-butyl (3-(3-(benzyloxy)prop-1-yn-1-yl)pyridin-4-yl)carbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
81%	With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In N,N-dimethyl-formamide; at 20℃;Inert atmosphere;	A resealable pressure vessel was charged with DMF(15.6 mL), tert-butyl (3- iodopyridin-4-yl)carbamate(5.0 g, 15.6 mmol), ((prop-2-yn-l- yloxy)methyl)benzene(3.04 g, 18.74 mmol), bis(triphenylphosphine)palladium(II) chloride(0.55 g, 0.78 mmol), copper(I) iodide(0.297 g, 1.56 mmol) and triethylamine(43.5 mL, 312 mmol) and the mixture was degassed by bubbling nitrogen through the mixture for several minutes. The reation mixture was stirred at ambient temperature overnight, diluted with ethyl acetate, washed twice with saturated ammonium chloride solution and once with brine. The combined organic phases were dried over sodium sulfate, filtered and evaporated to dryness. The crude material was purified by silica gel chromatography, eluting with a gradient from 20- 50% EtOAc in hexanes. The major peak was collected, affording tert-butyl (3-(3- (benzyloxy)prop-l-yn-l-yl)pyridin-4-yl)carbamate (4.27g, 81%). 1H NMR (400MHz, CHLOROFORM-d) delta = 8.56 (s, 1H), 8.49 - 8.34 (m, 1H), 8.14 (d, J=5.8 Hz, 1H), 7.51 - 7.32 (m, 6H), 4.71 (s, 2H), 4.51 (s, 2H), 1.56 (s, 9H).

Reference： [1]Patent: WO2015/191401,2015,A1 .Location in patent: Page/Page column 75

61
[ 4039-82-1 ]
[ 211029-67-3 ]
tert-butyl 2-((benzyloxy)methyl)-1H-pyrrolo[3,2-c]pyridine-1-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
81%	With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In N,N-dimethyl-formamide; at 65℃; for 48h;Inert atmosphere;	Tert-butyl 2-((benzy loxy)methyl)- 1 H-pyrrolo [3 ,2-c]pyridine- 1 -carboxylate was also prepared by the following alternate method: To a stirred solution of tert- butyl (3-iodopyridin-4-yl)carbamate (230 g, 718 mmol) in DMF (2.3L) was added ((prop-2-yn-l-yloxy)methyl)benzene (126 g, 862 mmol). The mixture was purged with nitrogen for 15min at which point copper(I) iodide (13.68 g, 71.8 (mmol),triethylamine (2.003 L, 1.44E+04 mmol) and bis(triphenylphosphine)palladium(II) chloride (25.2 g, 35.9 mmol) were added and the mixture purged again with nitrogen for 15min. The reaction mixture was heated to 65 C for 24h, at which point TLC (40% EtOAc in petroleum ether) showed some remaining intermediate, so the reaction mixture was re-heated to the same (0379) temperature for an additional 24h. The reaction mixture was then cooled to ambient temperature and concentrated to remove DMF. The residue was diluted with ethyl acetate (3.0 L) and quenched with saturated ammonium chloride solution. The phases were separated, the organics washed with brine and evaporated to afford the crude product, which was purified by silica gel chromatography, eluting with 25-80%) of EtOAc in petroleum ether. Mixed fractions were re-purified under the same conditions, and the pure fractions from both columns were combined to afford tert- butyl 2-((benzyloxy)methyl)-l H-pyrrolo [3, 2-c]pyridine-l -carboxylate (200g, 81%). LC/MS Method A: Retention time = 2.44min, M+H= 339.0.
80%	With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In N,N-dimethyl-formamide; at 65℃; for 24h;Sealed tube;	In a sealed tube, <strong>[211029-67-3]ter<strong>[211029-67-3]t-butyl (3-iodopyridin-4-yl)carbamate</strong></strong> 23 (0.5 g, 1.562 mmol), DMF (1.562 ml), ((prop-2-yn-1-yloxy)methyl)benzene 12 (0.261 ml, 1.874 mmol), PdCl2(Ph3P)2 (0.055 g, 0.078 mmol), copper(I) iodide (0.030 g, 0.156 mmol) and TEA (4.35 ml, 31.2 mmol) were added. The mixture was allowed to age overnight at 65 C. The reaction mixture was then partitioned between ethyl acetate and saturated ammonium chloride. The layers were separated and the organic layer was washed twice more with ammonium chloride. The combined organics were dried over sodium sulfate, filtered and evaporated to afford a brown oil. The mixture was purified by silica gel chromatography eluting with 20-50% EtOAc in hexanes, affording tert-butyl 2-((benzyloxy)methyl)-1H-pyrrolo[3,2-c]pyridine-1-carboxylate (0.423 g, 80%). 1H NMR (400MHz, CHLOROFORM-d) delta = 8.87 (d, J=0.8 Hz, 1H), 8.46 (d, J=5.8 Hz, 1H), 7.99 (d, J=6.0 Hz, 1H), 7.51 - 7.31 (m, 5H), 6.83 (s, 1H), 4.93 (d, J=1.3 Hz, 2H), 4.71 (s, 2H), 1.70 (s, 9H).

Reference： [1]Organic Process Research and Development,2018,vol. 22,p. 1276 - 1281
[2]Patent: WO2015/191401,2015,A1 .Location in patent: Page/Page column 77
[3]Tetrahedron Letters,2018,vol. 59,p. 751 - 754

62
[ 4039-82-1 ]
[ 25015-63-8 ]
[ 114653-18-8 ]

Yield	Reaction Conditions	Operation in experiment
87%	With Schwartz's reagent; triethylamine at 60℃; for 16h; Inert atmosphere;
82%	Stage #1: 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane With C₃₂H₄₁CuN₂O₂S In toluene at 20℃; for 0.25h; Schlenk technique; Inert atmosphere; Stage #2: Benzyl propargyl ether In toluene at 20℃; for 2h; Schlenk technique; Inert atmosphere; stereoselective reaction;
76%	With (1,3-bis(2,6-di-iso-propylphenyl)-4,5-dihydroimidazol-2-ylidene) copper chloride; tris-tert-butylphosphinimide, lithium salt In benzene at 20℃; for 13h; Glovebox; Inert atmosphere; stereoselective reaction;	III. Procedure for the Cu(I)-Catalyzed Alkyne Hydroboration Reaction 1. Cu (I) catalyzed hydroboration of terminal alkyne (Table 2) General procedure: In an N2 charged glove box with oxygen and water levels ≤0.1 ppm, to an oven-dried screwed vial were added SIPrCuCl (c8) (4.9 mg, 5 mol%, 0.01 mmol), tri(t-Butyl)phosphoranimide (1b) (2.2 mg, 5 mol%, 0.01 mmol), Pinacolborane (1c) (28 mg, 0.22 mmol, 1.1 eq.), terminal alkyne (1) (0.2 mmol, 1 eq.) and benzene (2 mL, 0.1 M). The formed reaction mixture was kept stirring for 13-15 hours in glove box. Then the dark brown reaction mixture was taken out from glove box the solvent was removed by rotary evaporator. The solvent mixture (Hexane:Ethyl acetate) was added into the reaction residue as eluent then kept stirring for about 30 mins under room temperature until the precipitate was formed. The mixture was further filtered through a short pad of silica gel to get colorless filtrate. Organic solvents were removed under reduced pressure and desired product was obtained after dryness under vacuum without further purification.

67%	With Schwartz's reagent; triethylamine at 65℃;	2 Step 2 Into a 250-mL round-bottom flask, was placed a mixture of [(prop-2-yn-1-yloxy)methyl]benzene (10 g, 68.4 mmol, 1.00 equiv), pinacolborane (10 mL), ZrCp2HCl (2 g), triethylamine (850 mg, 8.40 mmol, 0.12 equiv). The resulting solution was stirred for 16 hours at 65° C. in an oil bath. The resulting mixture were quenched with water (30 mL), then was extracted with ethyl acetate (50 mL3), and the organic layers combined. The resulting mixture was washed with brine (50 mL1). The resulting mixture was concentrated under vacuum. The residue was applied onto a silica gel column eluting with ethyl acetate/petroleum ether (1:1). This resulted in 12.5 g (67%) of 2-[(1E)-3-(benzyloxy)prop-1-en-1-yl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane as a yellow solid.
58%	With Schwartz's reagent; triethylamine at 60℃; for 12h;
48%	With lithium hexamethyldisilazane In toluene at 100℃; for 24h; Inert atmosphere; Glovebox; Schlenk technique;
	With Schwartz's reagent at 60℃; for 18h; Inert atmosphere;

Reference： [1]Martínez, Jose I.; Smith, Joshua J.; Hepburn, Hamish B.; Lam, Hon Wai [Angewandte Chemie - International Edition, 2016, vol. 55, # 3, p. 1108 - 1112][Angew. Chem., 2016, vol. 55-128, # 3, p. 1120 - 1124]
[2]Jang, Won Jun; Kang, Byung-Nam; Lee, Ji Hun; Choi, Yoon Mi; Kim, Chong-Hyeak; Yun, Jaesook [Organic and Biomolecular Chemistry, 2019, vol. 17, # 21, p. 5249 - 5252]
[3]Bai, Tao; Yang, Yanhui; Han, Chao [Tetrahedron Letters, 2017, vol. 58, # 15, p. 1523 - 1527]
[4]Current Patent Assignee: ARVINAS; ROCHE HOLDING AG - US2019/300521, 2019, A1 Location in patent: Paragraph 0811-0812
[5]Yi, Cheng-Bo; She, Zhi-Ying; Cheng, Yong-Feng; Qu, Jin [Organic Letters, 2018, vol. 20, # 3, p. 668 - 671]
[6]Liu, Jichao; Wu, Caiyan; Hu, Tinghui; Yang, Wei; Xie, Yaoyao; Shi, Yinyin; Liu, Qianrui; Shao, Yinlin; Zhang, Fangjun [Journal of Organic Chemistry, 2022, vol. 87, # 5, p. 3442 - 3452]
[7]Mennie, Katrina M.; Banik, Steven M.; Reichert, Elaine C.; Jacobsen, Eric N. [Journal of the American Chemical Society, 2018, vol. 140, # 14, p. 4797 - 4802]

63
[ 504-29-0 ]
[ 4039-82-1 ]
3-((benzyloxy)methyl)-2-iodoimidazo[1,2-a]pyridine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	With copper (I) iodide; iodine; oxygen In acetonitrile at 80℃; regioselective reaction;
70%	Stage #1: pyridine-2-amine; Benzyl propargyl ether With copper (I) iodide; iodine; β‐cyclodextrin In lithium hydroxide monohydrate at 20℃; for 0.5h; Green chemistry; Stage #2: In lithium hydroxide monohydrate at 90℃; for 4h; Green chemistry;	General procedure and characterization data for the 2-iodoimidazo[1,2-a]pyridines as listed in Table3 is exemplified for 6a General procedure: A suspension of 2-aminopyridine 5 (50mg, 1.0mmol), phenylacetylene 1 (54mg, 1.0mmol), iodine (187mg, 1.5mmol), CuI (10mol %) in β-cyclodextrin (1.0mol %) and water (5mL) was stirred for 30minat room temperature, a red homogeneous solution was formed, which was transferred to heating at 90°C for 4h. After the completion of reaction as monitored by TLC, the reaction was further diluted with water (10mL). The aqueous solution was extracted with EtOAc (3×10mL) and combined organic layer was washed with saturated Na2S2O3 solution, dried over anhydrous Na2SO4, and evaporated in vacuum. The residue was purified by column chromatography (silica gel, 30:70, v/v, EtOAc in petroleum ether) to afford the desired product.
	With copper (I) iodide; iodine In acetonitrile at 80℃;

Reference： [1]Dheer, Divya; Reddy, K. Ranjith; Rath, Santosh K.; Sangwan; Das, Parthasarthi; Shankar, Ravi [RSC Advances, 2016, vol. 6, # 44, p. 38033 - 38036]
[2]Dheer, Divya; Rawal, Ravindra K.; Singh, Virender; Sangwan; Das, Parthasarathi; Shankar, Ravi [Tetrahedron, 2017, vol. 73, # 30, p. 4295 - 4306]
[3]Singh, Davinder; Yodun, Tenzen; Kumar, Gulshan; Ahmad Tali, Javeed; Tiwari, Harshita; Singh, Jasvinder; Nargotra, Amit; Samykutty, Abhilash; Singh, Shashank; Shankar, Ravi [Bioorganic Chemistry, 2022, vol. 125]

64
[ 1603-41-4 ]
[ 4039-82-1 ]
3-((benzyloxy)methyl)-2-iodo-6-methylimidazo[1,2-a]pyridine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With copper (I) iodide; iodine; oxygen In acetonitrile at 80℃; regioselective reaction;
80%	Stage #1: (5-methyl-pyridin-2-yl)amine; Benzyl propargyl ether With copper (I) iodide; iodine; β‐cyclodextrin In lithium hydroxide monohydrate at 20℃; for 0.5h; Green chemistry; Stage #2: In lithium hydroxide monohydrate at 90℃; for 4h; Green chemistry;	General procedure and characterization data for the 2-iodoimidazo[1,2-a]pyridines as listed in Table3 is exemplified for 6a General procedure: A suspension of 2-aminopyridine 5 (50mg, 1.0mmol), phenylacetylene 1 (54mg, 1.0mmol), iodine (187mg, 1.5mmol), CuI (10mol %) in β-cyclodextrin (1.0mol %) and water (5mL) was stirred for 30minat room temperature, a red homogeneous solution was formed, which was transferred to heating at 90°C for 4h. After the completion of reaction as monitored by TLC, the reaction was further diluted with water (10mL). The aqueous solution was extracted with EtOAc (3×10mL) and combined organic layer was washed with saturated Na2S2O3 solution, dried over anhydrous Na2SO4, and evaporated in vacuum. The residue was purified by column chromatography (silica gel, 30:70, v/v, EtOAc in petroleum ether) to afford the desired product.
	With copper (I) iodide; iodine In acetonitrile at 80℃;

Reference： [1]Dheer, Divya; Reddy, K. Ranjith; Rath, Santosh K.; Sangwan; Das, Parthasarthi; Shankar, Ravi [RSC Advances, 2016, vol. 6, # 44, p. 38033 - 38036]
[2]Dheer, Divya; Rawal, Ravindra K.; Singh, Virender; Sangwan; Das, Parthasarathi; Shankar, Ravi [Tetrahedron, 2017, vol. 73, # 30, p. 4295 - 4306]
[3]Singh, Davinder; Yodun, Tenzen; Kumar, Gulshan; Ahmad Tali, Javeed; Tiwari, Harshita; Singh, Jasvinder; Nargotra, Amit; Samykutty, Abhilash; Singh, Shashank; Shankar, Ravi [Bioorganic Chemistry, 2022, vol. 125]

65
[ 694-59-7 ]
[ 4039-82-1 ]
[ 82113-65-3 ]
1-((3-(benzyloxy)prop-1-en-2-yl)oxy)pyridin-1-ium bis((trifluoromethyl)sulfonyl)amide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		Pre-prepared compound A (1.2 equiv., 90.2 mg) was added in sequence to a 4 ml reaction flask.Substrate alkyne 1i (0.2 mmol, 20.0 mg),PPh3AuNTf2 (2.5%, 3.7mg),HFIP (0.2 ml), stirring at room temperature for 2.5 hours.Feed 1.6ml of benzene, heat up to 90 C,Stir the reaction for 12 hours,TLC monitoring reaction is completed,Flash column chromatography (eluent petroleum ether: ethyl acetate = 15:1) gave a colorless oily material with a yield of 55%.

Reference： [1]Organic and Biomolecular Chemistry,2019,vol. 17,p. 966 - 972
[2]Journal of the American Chemical Society,2016,vol. 138,p. 5515 - 5518
[3]Patent: CN108383706,2018,A .Location in patent: Paragraph 0034; 0052-0054
[4]Journal of Organic Chemistry,2018,vol. 83,p. 10051 - 10059

66
[ 4039-82-1 ]
[ 552-79-4 ]
[ 78008-36-3 ]
[ 54010-75-2 ]
(R)-4-(benzyloxy)-1-[(R)-1,4-dioxaspiro[4.5]decan-2-yl]but-2-yn-1-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
79%	Stage #1: (-)-N-methylephedrine; zinc trifluoromethanesulfonate With triethylamine In toluene at 25℃; for 3h; Inert atmosphere; Stage #2: Benzyl propargyl ether In toluene at 25℃; for 0.583333h; Inert atmosphere; Stage #3: (R)-2,3-cyclohexylideneglyceraldehyde In toluene at 25℃; for 2.5h; Inert atmosphere;	(R)-4-(Benzyloxy)-1-[(R)-1,4-dioxaspiro[4.5]decan-2-yl]but-2-yn-1-ol (7) A 250 mL flask was charged with Zn(OTf)2 (6.73 g, 18.48 mmol) andheated to 120 °C under high vacuum for 14 h. After cooling to r.t., anhydtoluene (50 mL) followed by (-)-N-methylephedrine (3.68 g,20.54 mmol) and Et3N (3.2 mL, 22.59 mmol) were added and the resultantinhomogeneous mixture was stirred for 3 h at r.t. under argon.Alkyne 9 (3 g, 20.54 mmol) dissolved in anhyd toluene (15 mL) wasadded over 5 min and then the reaction mixture was stirred for 30min. Next, the aldehyde 8 (3.49 g, 20.54 mmol) (dissolved in approximately5 mL of anhyd toluene) was added over 3 min. After 2.5 h, TLC(30% EtOAc-hexane) showed the absence of aldehyde. The mixturewas diluted with Et2O and quenched with sat. aq NH4Cl. The aqueousphase was extracted with Et2O (3 ×). The combined organic phaseswere washed with brine and dried (Na2SO4). After evaporation of thevolatiles, column chromatography (hexane-EtOAc, 7:3) afforded thealcohol 7 (5.11 g, 17.38 mmol, 79%) as a colorless liquid; [α]D20 +2.32(c 0.35, CHCl3). The Mosher esters 7a and 7b (see below) were preparedby the known procedure.6IR (neat): 3423, 2935, 2858, 1450, 1364, 1098, 929, 741, 699 cm-1.1H NMR (500 MHz, CDCl3): δ = 7.38-7.27 (m, 5 H), 4.59 (s, 2 H), 4.38-4.33 (m, 1 H), 4.22-4.17 (m, 3 H), 4.10 (dd, J = 8.8, 6.5 Hz, 1 H), 4.10(dd, J = 8.8, 5.1 Hz, 1 H), 2.50 (br s, 1 H), 1.71-1.50 (m, 8 H), 1.49-1.33(m, 2 H).13C NMR (125 MHz, CDCl3): δ = 137.2, 128.4 (2 C), 128.0 (2 C), 127.9,111.1, 83.7, 82.2, 78.3, 71.6, 65.7, 64.4, 57.3, 36.5, 34.6, 25.0, 23.9,23.7.MS (ESI): m/z = 339 [M + Na]+.ESI-HRMS: m/z [M + H]+ calcd for C19H25O4: 317.1747; found:317.1745.

Reference： [1]Reddy, K. Siva Nagi; Reddy, A. Yugendar; Sabitha, Gowravaram [Synthesis, 2016, vol. 48, # 21, p. 3812 - 3820]

67
[ 4039-82-1 ]
[ 75872-61-6 ]
N,N-bis[4-(benzyloxy)-2-butynyl]-N-(tert-butyl)amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
93%	With copper(l) chloride In toluene at 80℃; for 6h; Schlenk technique; Inert atmosphere;	4.2. Preparation of N,N-bis(3-phenyl-2-propynyl)amines 3a-d and di(alkadiynyl) mines 5a-f General procedure: A 10 mL Schlenk tube equipped with a magnetic stirring bar was charged with 1,5,3-dioxazepanes 1a-d (1 mmol), terminal acetylene (2 mmol) and catalyst CuCl (0.05 mol %) in toluene (5 mL) and than stirred under an argon atmosphere at 80°C for 6 h. The mixture was cooled to r.t., the catalyst was removed from the reaction mixture by filtration through a layer of silica gel and the filtrate was dried over sodium sulfate; the solvent was evaporated under reduced pressure. The crude mixture was puried by column chromatography on silica gel to give the product.

Reference： [1]Khabibullina, Guzel R.; Zaynullina, Firuza T.; Karamzina, Diana S.; Ibragimov, Askhat G.; Dzhemilev, Usein M. [Tetrahedron, 2017, vol. 73, # 17, p. 2367 - 2373]

68
[ 4039-82-1 ]
C₁₃H₁₂SSe [ No CAS ]
C₂₃H₂₂OSSe [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%	Stage #1: Benzyl propargyl ether With cesiumhydroxide monohydrate In N,N-dimethyl-formamide at 20℃; for 0.5h; Inert atmosphere; Stage #2: C₁₃H₁₂SSe In N,N-dimethyl-formamide at 20℃; for 15h; Inert atmosphere; stereoselective reaction;	General Procedure for the preparation of (Z)-vinylic selenosulfides 3a-3ae: General procedure: Alkyne (0.2 mmol) was added, under nitrogen, to a solution of cesium hydroxide monohydrate (0.04 mmol) in DMF (2.0 mL). The resulting solution was stirred for 30 min at room temperature. After this time, unsymmetrical diorgano dichalcogenides (0.2 mmol) was added to the mixture solution under nitrogen. The reaction was stirred at room temperature, under nitrogen for 15 h. After this time, the mixture was diluted with water (3.0 mL), and extracted with diethyl ether (3.0 mL x 3). The combined organic phase was dried over Na2SO4, and concentrated under vacuum. The residue was purified by flash chromatography on silica gel (eluent hexane/ethyl acetate) to afford 3a-3ae.

Reference： [1]Peng, Lifen; Li, Rongzhen; Tang, Zilong; Chen, Jingyang; Yi, Rongnan; Xu, Xinhua [Tetrahedron, 2017, vol. 73, # 22, p. 3099 - 3105]

69
[ 4039-82-1 ]
(4-methoxyphenyl)(phenylselanyl)sulfane [ No CAS ]
C₂₃H₂₂O₂SSe [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	Stage #1: Benzyl propargyl ether With cesiumhydroxide monohydrate In N,N-dimethyl-formamide at 20℃; for 0.5h; Inert atmosphere; Stage #2: (4-methoxyphenyl)(phenylselanyl)sulfane In N,N-dimethyl-formamide at 20℃; for 15h; Inert atmosphere; stereoselective reaction;	General Procedure for the preparation of (Z)-vinylic selenosulfides 3a-3ae: General procedure: Alkyne (0.2 mmol) was added, under nitrogen, to a solution of cesium hydroxide monohydrate (0.04 mmol) in DMF (2.0 mL). The resulting solution was stirred for 30 min at room temperature. After this time, unsymmetrical diorgano dichalcogenides (0.2 mmol) was added to the mixture solution under nitrogen. The reaction was stirred at room temperature, under nitrogen for 15 h. After this time, the mixture was diluted with water (3.0 mL), and extracted with diethyl ether (3.0 mL x 3). The combined organic phase was dried over Na2SO4, and concentrated under vacuum. The residue was purified by flash chromatography on silica gel (eluent hexane/ethyl acetate) to afford 3a-3ae.

Reference： [1]Peng, Lifen; Li, Rongzhen; Tang, Zilong; Chen, Jingyang; Yi, Rongnan; Xu, Xinhua [Tetrahedron, 2017, vol. 73, # 22, p. 3099 - 3105]

70
[ 4039-82-1 ]
C₁₂H₉ClSSe [ No CAS ]
C₂₂H₁₉ClOSSe [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	Stage #1: Benzyl propargyl ether With cesiumhydroxide monohydrate In N,N-dimethyl-formamide at 20℃; for 0.5h; Inert atmosphere; Stage #2: C₁₂H₉ClSSe In N,N-dimethyl-formamide at 20℃; for 15h; Inert atmosphere; stereoselective reaction;	General Procedure for the preparation of (Z)-vinylic selenosulfides 3a-3ae: General procedure: Alkyne (0.2 mmol) was added, under nitrogen, to a solution of cesium hydroxide monohydrate (0.04 mmol) in DMF (2.0 mL). The resulting solution was stirred for 30 min at room temperature. After this time, unsymmetrical diorgano dichalcogenides (0.2 mmol) was added to the mixture solution under nitrogen. The reaction was stirred at room temperature, under nitrogen for 15 h. After this time, the mixture was diluted with water (3.0 mL), and extracted with diethyl ether (3.0 mL x 3). The combined organic phase was dried over Na2SO4, and concentrated under vacuum. The residue was purified by flash chromatography on silica gel (eluent hexane/ethyl acetate) to afford 3a-3ae.

Reference： [1]Peng, Lifen; Li, Rongzhen; Tang, Zilong; Chen, Jingyang; Yi, Rongnan; Xu, Xinhua [Tetrahedron, 2017, vol. 73, # 22, p. 3099 - 3105]

71
[ 4039-82-1 ]
[ 124201-01-0 ]
C₂₁H₁₉NOSSe [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87%	Stage #1: Benzyl propargyl ether With cesiumhydroxide monohydrate In N,N-dimethyl-formamide at 20℃; for 0.5h; Inert atmosphere; Stage #2: (2-Pyridylthio)phenyl selenide In N,N-dimethyl-formamide at 20℃; for 15h; Inert atmosphere; stereoselective reaction;	General Procedure for the preparation of (Z)-vinylic selenosulfides 3a-3ae: General procedure: Alkyne (0.2 mmol) was added, under nitrogen, to a solution of cesium hydroxide monohydrate (0.04 mmol) in DMF (2.0 mL). The resulting solution was stirred for 30 min at room temperature. After this time, unsymmetrical diorgano dichalcogenides (0.2 mmol) was added to the mixture solution under nitrogen. The reaction was stirred at room temperature, under nitrogen for 15 h. After this time, the mixture was diluted with water (3.0 mL), and extracted with diethyl ether (3.0 mL x 3). The combined organic phase was dried over Na2SO4, and concentrated under vacuum. The residue was purified by flash chromatography on silica gel (eluent hexane/ethyl acetate) to afford 3a-3ae.

Reference： [1]Peng, Lifen; Li, Rongzhen; Tang, Zilong; Chen, Jingyang; Yi, Rongnan; Xu, Xinhua [Tetrahedron, 2017, vol. 73, # 22, p. 3099 - 3105]

72
[ 136-95-8 ]
[ 4039-82-1 ]
3-((benzyloxy)methyl)-2-iodobenzo[d]imidazo[2,1-b]thiazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	Stage #1: 2-amino-benzthiazole; Benzyl propargyl ether With copper(l) iodide; iodine; β‐cyclodextrin In water at 20℃; for 0.5h; Green chemistry; Stage #2: In water at 90℃; for 4h; Green chemistry;	General procedure and characterization data for the 2-iodobenzoimidazo[2,1-b]thiazoles listed in Table4 as exemplified for 8a General procedure: A suspension of 2-aminobenzothiazole 7 (50mg, 1.0mmol), phenylacetylene 1 (34mg, 1.0mmol), iodine (84mg, 1.5mmol) and CuI (10mol %) and β-cyclodextrin (1.0mol %) in water (5mL) was stirred for 30minat room temperature, a red homogeneous solution was formed, after that reaction temperature was raised up to 90°C for 4h (reaction progress was monitored by TLC). After reaction was finished, the mixture was quenched with water. The aqueous solution was extracted with EtOAc (3×10mL) and combined organic layer was washed with saturated Na2S2O3 solution, dried over anhydrous Na2SO4, and evaporated in vacuum. The residue was purified by column (silica gel, 30:70 v/v EtOAc in petroleum ether) to afford the desired product.

Reference： [1]Dheer, Divya; Rawal, Ravindra K.; Singh, Virender; Sangwan; Das, Parthasarathi; Shankar, Ravi [Tetrahedron, 2017, vol. 73, # 30, p. 4295 - 4306]

73
[ 4039-82-1 ]
[ 25015-63-8 ]
C₁₆H₂₃BO₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%	With C₃₉H₆₅CuN₃P In benzene at 20℃; for 13h;	15 Example 15: The boron hydrogenation of propargylbenzyl ether catalyzed by complex B gave the product 2n in 76% yield.

Reference： [1]Current Patent Assignee: SHANXI UNIVERSITY - CN106243132, 2016, A Location in patent: Paragraph 0079; 0080

74
[ 4039-82-1 ]
[ 25015-63-8 ]
[ 126689-01-8 ]

Reference： [1]Organic Letters,2017,vol. 19,p. 3891 - 3894

75
[ 1122-96-9 ]
[ 4039-82-1 ]
[ 82113-65-3 ]
1-((3-(benzyloxy)prop-1-en-2-yl)oxy)pyridin-1-ium bis((trifluoromethyl)sulfonyl)amide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
79%		Prefabricated compound A, under ice bath conditions,In a vial containing 1 ml of dichloromethane,Followed by adding Tf2NH (1.1 equiv61.6mg),Pyridine nitrogen oxide (1.2 equiv 22.8 mg) was added and stirred at room temperature for 1 h,In addition to solvent solvent, retained.AgBF4 (10% 3.8 mg) was added sequentially to a 5 ml vial,Preformed compound A, 1h (0.2 mmol 25.2 mg),HFIP 0.2ml, the system is closed,At 65 C under the conditions of heating and stirring for 12 hours TLC monitoring is completed,Column chromatography eluent dichloromethane: methanol = 50: 1 as a colorless oily liquid,Yield 79%.

Reference： [1]Patent: CN107162967,2017,A .Location in patent: Paragraph 0077; 0078; 0079; 0080

76
[ 4039-82-1 ]
[ 2523-42-4 ]
C₂₉H₃₃BO₃ [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2017,vol. 139,p. 15316 - 15319

77
[ 4039-82-1 ]
[ 2523-42-4 ]
2-(3-(benzyloxy)prop-1-yn-1-yl)-9H-fluorene [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2017,vol. 139,p. 15316 - 15319

78
[ 13472-61-2 ]
[ 4039-82-1 ]
C₂₂H₃₀BNO₄ [ No CAS ]
C₂₂H₃₀BNO₄ [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2017,vol. 139,p. 15316 - 15319

79
[ 13472-61-2 ]
[ 4039-82-1 ]
5-(3-(benzyloxy)prop-1-yn-1-yl)-2-methoxypyridine [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2017,vol. 139,p. 15316 - 15319

80
[ 111-66-0 ]
[ 4039-82-1 ]
(E)-(((2-methylenedec-3-en-1-yl)oxy)methyl)benzene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
66%	With tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride; ethene In dichloromethane at 0 - 20℃; for 24h; Inert atmosphere; Schlenk technique;	1.2.12.1 General metathesis procedure General procedure: An inertized Schlenk flask was filled with 0.1 eq. of ruthenium catalyst and cooled to 0 °C. Itwas subsequently evacuated and flooded with ethylene. Then, 2.0 ml/mmol (regarding thealkyne) of dry CH2Cl2, 1.0 eq. of alkyne and 10.0 eq. of alkene were added and the reactionmixture was stirred at r.t. for 24 - 72 h. Residual catalyst was removed by stirring the reactionmixture over active charcoal.[13] The suspension was filtrated over silica and the solvent wasevaporated under reduced pressure. The crude product was purified via columnchromatography and the products were obtained as colourless oils.

Reference： [1]Ratsch, Friederike; Schmalz, Hans-Günther [Synlett, 2018, vol. 29, # 6, p. 785 - 792]

81
[ 4039-82-1 ]
(1aR,7aS,10aS,10bS,E)-5-(azidomethyl)-1a-methyl-8-methylene-2,3,6,7,7a,8,10a,10b-octahydrooxireno[2',3':9,10]cyclodeca[1,2-b]furan-9(1aH)-one [ No CAS ]
(1aR,7aS,10aS,10bS,E)-1a-methyl-8-methylene-5-((4-(phenoxymethyl)-1H-1,2,3-triazol-1-yl)methyl)-2,3,6,7,7a,8,10a,10b-octahydrooxireno[20,3':9,10]cyclodeca[1,2-b]furan-9(1aH)-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
88%	With copper(I) oxide In tetrahydrofuran; water at 20℃; for 2h; Inert atmosphere;	4.1.3 General procedure for synthesis of compounds 4a-4p, 6a-6f, 8a-8c, 10a-10c and 12a-12c General procedure: To a solution of compound 3 (1 equiv.) and corresponding alkynes (1.5 equiv.) in THF was added Cu2O-NPs, which was dispersed in H2O under an Ar atmosphere. The solution was stirred at room temperature for 2h, quenched with saturated aqueous NH4Cl, and extracted with EA (3×20mL). The combined organic layers were washed with saturated brine, dried over anhydrous Na2SO4, and concentrated to give an oily crude product, which was purified on a silica gel column [petroleum ether (PE):EA=1:1] to yield compounds 4a-4p, 6a-6f, 8a-8c, 10a-10c and 12a-12c.

Reference： [1]Ding, Yahui; Guo, Hongyu; Ge, Weizhi; Chen, Xinyi; Li, Shengzu; Wang, Mengmeng; Chen, Yue; Zhang, Quan [European Journal of Medicinal Chemistry, 2018, vol. 156, p. 216 - 229]

82
[ 4039-82-1 ]
[ 211029-67-3 ]
tert-butyl 2-(hydroxymethyl)-2,3-dihydro-1H-pyrrolo[3,2-c]pyridine-1-carboxylate [ No CAS ]
C₂₀H₂₄N₂O₃ [ No CAS ]

Reference： [1]Organic Process Research and Development,2018,vol. 22,p. 1276 - 1281

83
[ 4039-82-1 ]
[ 211029-67-3 ]
tert-butyl (3-(3-(benzyloxy)prop-1-yn-1-yl)pyridin-4-yl)carbamate [ No CAS ]
tert-butyl 2-((benzyloxy)methyl)-1H-pyrrolo[3,2-c]pyridine-1-carboxylate [ No CAS ]

Reference： [1]Organic Process Research and Development,2018,vol. 22,p. 1276 - 1281

84
[ 4039-82-1 ]
[ 139507-52-1 ]
ethyl 5-(benzyloxy)-2-oxopent-3-ynoate [ No CAS ]

Reference： [1]Chemistry - An Asian Journal,2018,vol. 13,p. 2838 - 2841

85
[ 1110650-02-6 ]
[ 4039-82-1 ]
methyl 3,4,6-tri-O-acetyl-2-[(4-(benzyloxymethyl)-1H-1,2,3-triazole-1-yl)]-2-deoxy-D-glucopyranoside [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
79%	With copper(ll) sulfate pentahydrate; sodium L-ascorbate In water; N,N-dimethyl-formamide at 70℃; for 0.166667h; Microwave irradiation; Sealed tube;	General procedure for the synthesis of compounds 5a-g, 5i-jand 5l: General procedure: [28] Compound 3 containing the azide group (1.0 eq.) wasdissolved in DMF (0.3 mL), followed by the addition of sodium ascorbate(0.1 eq.), CuSO4 (10% aqueous solution; 0.04 eq.) and one of theacetylene derivatives (1.0 eq.). The mixture was stirred for 10 min at70 °C under microwave irradiation (sealed microwave tube) (150 W).The reaction mixture was then concentrated under reduced pressure byco-evaporation with toluene, diluted in water (20 mL) and extractedwith EtOAc (3 x 25 mL). The combined organic layers were dried overMgSO4, concentrated under reduced pressure and purified by flashchromatography [Hexane:EtOAc (1:1)] to afford the desired products(5a-g, 5i-j and 5l).

Reference： [1]Igual, Michelle O.; Nunes, Paulo S.G.; da Costa, Rafael M.; Mantoani, Susimaire P.; Tostes, Rita C.; Carvalho, Ivone [Carbohydrate Research, 2019, vol. 471, p. 43 - 55]

86
[ 1217-89-6 ]
[ 4039-82-1 ]
C₂₅H₂₁NO₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With 1,4-diaza-bicyclo[2.2.2]octane; copper(II) tungstate In water at 60℃; Green chemistry;	General procedure for the preparation of 3-hydroxy-3-(phenylethynyl)indolin-2-ones (3a-3u) General procedure: To a mixture of isatin (1 equiv.) and phenyl acetylene (1.2 equiv.) in water (3 mL), CuWO4 (10 mol%) and DABCO (40 mol%) were added at room temperature and the mixture was heated at 60 °C for 2 to 5 h. After completion of reaction (monitoring by TLC) mixture was cooled to room temperature and extracted with EtOAc (2×10 mL). The organic layers were washed with brine, dried using sodium sulfate. Evaporation of the solvent gave the crude product which was purified by silica gel column chromatography to give 3-hydroxy-3-(phenylethynyl)indolin-2-ones (3a-3u).

Reference： [1]Paplal, Banoth; Sathish, Kota; Nagaraju, Sakkani; Kashinath, Dhurke [Catalysis Communications, 2020, vol. 135]

87
[ 4039-82-1 ]
[ 73183-34-3 ]
[ 114653-18-8 ]

Yield	Reaction Conditions	Operation in experiment
81%	With copper(I) oxide supported on ceria nanoparticle In ethanol at 90℃; for 1h; Inert atmosphere; Schlenk technique;	Substrate scope investigations with the Cu1-O(I)/CeO2 catalyst General procedure: In a typical procedure, B2Pin2 (0.7 mmol, 177.4 mg) and Cu1-O(I)/CeO2 (Cu = 0.5 mol %, 7.6 mg) were placed in adried Schlenk tube equipped with a stir bar. After evacuation under vacuum and flushing with N2 for three times,alkyne substrate (0.5 mmol) and ethanol (2.0 mL) were injected under the atmosphere of N2. The mixture wasultrasonically vibrated to form a uniform suspension and then stirred at 90oC for 1.0 h. Upon completion, the reactionmixture was analyzed by GC-MS to determine the selectivity of vinylboronate products. To determine the isolatedyield of the target product, the reaction mixture was centrifuged to remove the catalyst, and the supernate wasconcentrated in vacuum. The residue was purified by flash column chromatography on silica gel with petroleumether/ethyl acetate as eluent.

Reference： [1]Zhang, Jian; Wang, Ziyun; Chen, Wenxing; Xiong, Yu; Cheong, Weng-Chon; Zheng, Lirong; Yan, Wensheng; Gu, Lin; Chen, Chen; Peng, Qing; Hu; Wang, Dingsheng; Li, Yadong [Chem, 2020, vol. 6, # 3, p. 725 - 737]

88
[ 4039-82-1 ]
(R)-1-(3-(4-amino-3-iodo-1H-pyrazolo[3,4-d]pyrimidin-1-yl)-piperidin-1-yl)prop-2-en-1-one [ No CAS ]
(R)-1-(3-(4-amino-3-(3-(benzyloxy)prop-1-yn-1-yl)-1H-pyrazolo[3,4-d]pyrimidin-1-yl)piperidin-1-yl)prop-2-en-1-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
84.9%	With copper(l) iodide; tetrakis(triphenylphosphine) palladium⁽⁰⁾; triethylamine In N,N-dimethyl-formamide at 80℃; for 15h; Inert atmosphere;	68.2 Step 2: Synthesis of Compound (R) -1- (3- (4-amino-3- (3- (benzyloxy) prop-1-yn-1-yl) -1H-pyrazolo [3,4-d ] pyrimidin-1-yl) piperidin-1-yl) prop-2-en-1-one (R) -1- (3- (4-Amino-3-iodo-1H-pyrazolo [3,4-d] pyrimidin-1-yl) piperidin-1-yl) prop-2-ene- 1-ketone (180mg, 0.45mmol) dissolved in DMF (12mL),Continue to add ((prop-2-yn-1-yloxy) methyl) benzene (120mg, 0.81mmol), cuprous iodide (17mg, 0.09mmol), triethylamine (30mg, 0.30mmol) and tetrakis ( Triphenylphosphine) palladium (26 mg, 0.022 mmol).Under nitrogen protection, heat to 80 ° C for 15h, stop heating, cool to room temperature, filter through celite, and concentrate the solvent.Saturated brine (100 mL) was added, extracted with dichloromethane (50 mL × 3), dried over anhydrous sodium sulfate, filtered, and concentrated.Silica gel column chromatography was separated and purified (DCM / MeOH (v / v) = 50/1) to obtain 160 mg of brown solid, yield: 84.9%.

Reference： [1]Current Patent Assignee: SHENZHEN DONGYANGGUANG INDUSTRIAL DEVELOPMENT CO LTD - CN107344940, 2020, B Location in patent: Paragraph 1201-1203; 1206-1209

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CAS No. :	4039-82-1	MDL No. :	MFCD00483987
Formula :	C₁₀H₁₀O	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	PAQVEXAFKDWGOT-UHFFFAOYSA-N
M.W :	146.19	Pubchem ID :	6917484
Synonyms :

Num. heavy atoms :	11
Num. arom. heavy atoms :	6
Fraction Csp3 :	0.2
Num. rotatable bonds :	3
Num. H-bond acceptors :	1.0
Num. H-bond donors :	0.0
Molar Refractivity :	45.08
TPSA :	9.23 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) :	-5.75 cm/s

Log Po/w (iLOGP) :	2.28
Log Po/w (XLOGP3) :	2.03
Log Po/w (WLOGP) :	1.76
Log Po/w (MLOGP) :	2.4
Log Po/w (SILICOS-IT) :	2.67
Consensus Log Po/w :	2.23

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[ 4039-82-1 ]

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Lipinski :	0.0
Ghose :	None
Veber :	0.0
Egan :	0.0
Muegge :	2.0
Bioavailability Score :	0.55

Log S (ESOL) :	-2.23
Solubility :	0.859 mg/ml ; 0.00588 mol/l
Class :	Soluble
Log S (Ali) :	-1.85
Solubility :	2.06 mg/ml ; 0.0141 mol/l
Class :	Very soluble
Log S (SILICOS-IT) :	-3.01
Solubility :	0.144 mg/ml ; 0.000982 mol/l
Class :	Soluble

PAINS :	0.0 alert
Brenk :	1.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	1.95

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

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P378
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P391	Collect spillage. Hazardous to the aquatic environment
P301 + P310	IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician.
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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.
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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:
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[ CAS No. 4039-82-1 ] {[proInfo.proName]}

Quality Control of [ 4039-82-1 ]

Related Doc. of [ 4039-82-1 ]

Product Details of [ 4039-82-1 ]

Calculated chemistry of [ 4039-82-1 ]

Physicochemical Properties

Pharmacokinetics

Lipophilicity

Druglikeness

Water Solubility

Medicinal Chemistry

Safety of [ 4039-82-1 ]

Application In Synthesis of [ 4039-82-1 ]

[ 4039-82-1 ] Synthesis Path-Upstream 1~3

[ 4039-82-1 ] Synthesis Path-Downstream 1~88

Related Functional Groups of [ 4039-82-1 ]

Aryls

Alkynes

Ethers

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry

Related Functional Groups of
[ 4039-82-1 ]