Name: 65423-56-5|(3-Bromophenoxy)(tert-butyl)dimethylsilane|98%
Brand: Ambeed
SKU: A773991
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1
[ 591-20-8 ]
[ 18162-48-6 ]
[ 65423-56-5 ]

Yield	Reaction Conditions	Operation in experiment
100%	With 1H-imidazole In N,N-dimethyl-formamide at 25℃; for 16h;
100%	With 1H-imidazole
100%	With 1H-imidazole In dichloromethane at 20℃; for 4h;

100%	With 1H-imidazole In N,N-dimethyl-formamide at 20℃; for 3h;	51.1 A mixture of 3-bromophenol (730mg, 4.22mmol), TBSCl (700mg, 4.64mmol), and imidazole (330mg, 4.85mmol) in DMF was stirred for 3 hours at room temperature. The mixture was poured into water and extracted with Et2O. The organic layer was dried over anhydrous MgSC^, filtered, and concentrated under reduced pressure to give a TBS ether with a quantitative yield.
99%	With 1H-imidazole In N,N-dimethyl-formamide at 25℃; for 18h;
99%	With 1H-imidazole In dichloromethane at 20℃; for 16h; Cooling with ice;	1 Step 1; (3-bromophenoxy)(tert-butyl)dimethylsilane A solution of 3-bromophenol (100.00 g, 580 mmol) and imidazole (78.70 g, 1.16 mmol) in DCM (1.2 E) was added drop-wise to a cooled (ice/NaC1 bath) solution oftenbutyldimethylsilyl chloride (95.83 g, 630 mmol) in DCM (100 mE). The reaction mixture was stirred at room temperature for 16 hours. The reaction mixture was washed with water, brine and the organic phase was evaporated under reduced pressure. The residue was purified by flash column chromatography (eluent-100% iso-hexane to 5:1 iso-hexane/ethyl acetate) to afford the title product (163.7 g, 99%). 1H NMR (400 MHz, CDC13) ö 7.12-7.10 (m, 2H), 7.03 (ddd, J=2.2, 1.4,0.8Hz, 1H), 6.81-6.76 (m, 1H), 1.00 (s, 9H), 0.22 (s, 6H).
99%	With 1H-imidazole In dichloromethane at 20℃; for 24h; Sealed tube;
98.4%	With 1H-imidazole In dichloromethane at 20℃;	1.A A solution of 3-bromophenol (400 g, 2.31 mol), tert-butylchlorodimethylsilane (391 g, 2.54 mol), and imidazole (346 g, 5.08 mol) in 5000 mL of dichloromethane was stirred overnight at room temperature. The reaction solution was poured into water (2000 mL) and the layers EPO separated. The organic layer was washed with IN aqueous sodium hydroxide solution (3 X 1500 mL) and water (2 X 1500 rnL) before passing through a pad of silica gel (400 g, silica 60, 230-400 mesh). The silica gel was washed with dichloromethane (2 X 500 mL), the filtrates combined and the solvent removed under reduced pressure to give 3-(bromophenoxy)-tert- butyldimethylsilane (669 g, 98.4%) as a clear pale yellow liquid. NMR (300 MHz, CDCl3): δ0.2 (s,6H); 1.0 (s,9H); 6.75 (m,lH); 7.0 (br s, IH); 7.1 (m,2H).
98.4%	With 1H-imidazole In dichloromethane at 20℃;	1.A Method A - Alkylation with phenol protection A solution of 3-bromophenol (400 g, 2.31 mol), tert-butylchlorodimethylsilane (391 g, 2.54 mol), and imidazole (346 g, 5.08 mol) in 5000 mL of dichloromethane was stirred overnight at room temperature. The reaction solution was poured into water (2000 mL) and the layers separated. The organic layer was washed with IN aqueous sodium hydroxide solution (3 X 1500 mL) and water (2 X 1500 mL) before passing through a pad of silica gel (400 g, silica 60, 230-400 mesh). The silica gel was washed with dichloromethane (2 X 500 mL), the filtrates combined and the solvent removed under reduced pressure to give 3- (bromophenoxy)-tert-butyldimethylsilane (669 g, 98.4%) as a clear pale yellow liquid. MR (300 MHz, CDC13): δ 0.2 (s,6H); 1.0 (s,9H); 6.75 (m, lH); 7.0 (br s, 1H); 7.1 (m,2H).
98.4%	With 1H-imidazole In dichloromethane at 20℃;	1 [0080] A solution of 3-bromophenol (400 g, 2.31 mol), tert-butylchlorodimethylsilane (391 g, 2.54 mol), and imidazole (346 g, 5.08 mol) in 5000 mL of dichloromethane was stirred overnight at room temperature. The reaction solution was poured into 2000 mL of water and the layers were separated. The organic layer was washed with iN aqueous sodium hydroxide solution (3 X 1500 mL) and water (2 X 1500 mL) before passing through a pad of silica gel (400 g, silica 60, 230-400 mesh). The silica gel was washed with dichloromethane (2 X 500 mL), the filtrates were combined and the solvent removed under reduced pressure to give 669 g (98.4%) of 3-(bromophenoxy)-tert-butyldimethylsilane as a clear pale yellow liquid. NMR (300 IVIHz, CDC13): 0.2 (s,6H); 1.0 (s,9H); 6.75 (m,1H); 7.0 (br s, 1H); 7.1 (m,2H).
97%	With 1H-imidazole In N,N-dimethyl-formamide at 0℃; for 6h;	1 Synthesis of (3 -Bromophenoxy)-tert-butyl-dimethyl-silane Tert-butyl dimethylsilyl chloride (3.150 g, 21.00 mmol) was added to a solution of imidazole (1.900 g, 27.94 mmol) and 3-bromophenol (1.520 mL, 14.01 mmol) in anhydrous DMF(40 mL) at 0° C.The reaction mixture was stirred for 6 hrs. Upon completion of the reaction, 5% aqueous NaHCO3 (20 ml) was added to the reaction mixture. The products were extracted with hexanes (2 x 50 mL) and concentrated under reduced pressure. Purification by flash column chromatography (silica gel, hexanes 100%) afforded (3-bromo-phenoxy)-tert-butyl-dimethyl-silane (3.905 g, 13.59 mmol, 97% yield) as a colorless oil. ‘H NMR (500 MHz, CDCI3) 6 7.10-7.06 (2H, m), 7.0 1-7.00 (IH, m), 6.78-6.74 (IH, m),0.98 (9H, s), 0.20 (6H, s). ‘3C NMR (125 MHz, CDCI3) 6156.67, 130.55, 124.61, 123.66, 122.61, 118.96,25.75, 18.33, -4.32.
97%	With 1H-imidazole In N,N-dimethyl-formamide at 0℃; for 6h; Inert atmosphere;	(3-Bromophenoxy)-tert-butyl-dimethyl-silane (1).1 Tert-butyl dimethylsilyl chloride (3.150 g, 21.00 mmol) was added to a solution ofimidazole (1.900 g, 27.94 mmol) and 3-bromophenol (1.520 mL, 14.01 mmol) in anhydrousDMF (40 mL) at 0° C. The reaction mixture was stirred for 6 hrs. Upon completion of thereaction, 5% aqueous NaHCO3 (20 ml) was added to the reaction mixture. The products wereextracted with hexanes (2 x 50 mL) and concentrated under reduced pressure. Purification byflash column chromatography (silica gel, hexanes 100%) afforded (3-bromo-phenoxy)-tertbutyl-dimethyl-silane (3.905 g, 13.59 mmol, 97% yield) as a colorless oil.
97%	With 1H-imidazole In dichloromethane at 20℃; Inert atmosphere;
96%	With 1H-imidazole In dichloromethane at 20℃; for 4h; Inert atmosphere;
91%	With 1H-imidazole In dichloromethane at 20℃;	1 10304] 3-l3romophenyl tert-butyldimethylsilyl ether (2) 10304] 3-l3romophenyl tert-butyldimethylsilyl ether (2):3-l3romophenol (6 mmol, 1.04 g), imidazole (10 mmol, 0.68 g) and TI3DMSC1 (6.6 mmol, 0.99 g) were dissolved in DCM (20 ml). The solution was allowed to stir at room temperature overnight. The solid generated during the reaction was filtered off and the solvent removed under reduced pressure. The resulting residue was subjected to flash chromatography (EtOAc/Hexanes=3%.-1 5%) giving compound 2 (1.56 g, 5.44 mmol, yield 91%). ‘H NMR (CDC13): ö 7.11-7.08 (m, 2H), 7.03-7.02 (m, 1H), 6.80-6.77 (m, 1H), 0.99 (s, 9H), 0.31 (s, 6H).
91.3%	With 1H-imidazole In dichloromethane at 20℃;	2 (3-Bromophenoxy) (tert-butyl)dimethylsilane (9) (3-Bromophenoxy) (tert-butyl)dimethylsilane (9) A round-bottom flask was charged with 3-bromophenol (8.65 g, 50.0 mmol, 1.0 eq.), tert-butyldimethylsilyl chloride (7.9 g, 52 mmol, 1.05 eq.), imidazole (3.6 g, 52 mmol, 1.05 eq.), and CH2Cl2 (70 mL). After stirring overnight at room temperature, the reaction was washed sequentially with 1.0 M HCl in H2O (50 mL) and 1.0 M NaOH in H2O (50 mL). The organics were collected, dried over Na2SO4, and concentrated under reduced pressure to afford the title compound as a colorless oil (13.12 g, 45.7 mmol, 91.3%). 1H NMR (500 MHz, CDCl3) δ 7.12-7.04 (m, 2H), 7.03-6.98 (m, 1H), 6.76 (ddq, J=6.5, 4.2, 2.2 Hz, 1H), 0.98 (s, 9H), 0.20 (s, 6H). 13C NMR (126 MHz, CDCl3) δ 156.68, 130.55, 124.61, 123.67, 122.61, 118.96, 25.76, 18.33, -4.31.
89%	With 1H-imidazole microwave irradiation;
	With 1H-imidazole In N,N-dimethyl-formamide for 20h; Ambient temperature;
	With 1H-imidazole 1.) CH₂Cl₂, 0 deg C, 10 min, 2.) CH₂Cl₂, room temperature, 14 h; Yield given. Multistep reaction;
	With 1H-imidazole In N,N-dimethyl-formamide at 25℃; for 3h;
	With 1H-imidazole In N,N-dimethyl-formamide at 20℃; for 18h;
	Stage #1: 3-Bromophenol With 1H-imidazole In dichloromethane at 0℃; for 0.166667h; Stage #2: tert-butyldimethylsilyl chloride In dichloromethane at 20℃;	TBS-protected 3-bromophenol; To a solution of 3-bromophenol (100 g, 0.6 mol) in dichloromethane (600 ml) was added imidazole (100 g, 1.46 mol) at 0°C. After 10 min, TBDMS-CI (96 g, 0.64 mol) was added, and the mixture was stirred at RT overnight. The mixture was then diluted with MTBE (1 L) and filtered. The filtrate was washed with sat. ammonium chloride (4 x 200 ml), sat. bicarb. (200 ml) and brine (200 ml), before being dried (MgS04), filtered and concentrated in vacuo to give the product as a yellow oil (156.6 g) that was used without further purification. 8H (CDC13; 250MHz) 7.10-6.77 (4H, m, aromatics), 0.99 (9H, s, C(CH3)3), 0.21 (6H, s, 2 x CH3).
	With 1H-imidazole In dichloromethane at 0 - 23℃; for 16h;	25 (Synthesis example 25) 50 parts of m-bromophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 30 parts of imidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 500 parts of dichloromethane (manufactured by Kanto Chemical Co., Ltd.) and cooled to 0 ° C., followed by tert. -Butyldimethylchlorosilane (manufactured by Tokyo Chemical Industry Co., Ltd.) 48 parts was dropped. After the dropping was completed, the temperature was raised to 23 ° C. and the mixture was stirred for 16 hours. After completion of the reaction, water was added to extract the organic layer, the solvent was concentrated, and the residue was separated and purified by silica gel column chromatography to obtain 74 parts of the compound represented by the formula (1-10).
	With 1H-imidazole In dichloromethane at 0 - 23℃; for 16h;	2 Colorant synthesis example 2 50 parts of m-bromophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 30 parts of imidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 500 parts of methylene chloride (manufactured by Kanto Chemical Co., Ltd.) and cooled to 0°C ,48 parts of tert-butyldimethylchlorosilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were added dropwise.After the dropwise addition, the temperature was raised to 23°C and stirred for 16 hours. After the reaction, water was added and the organic layer was extracted. After the solvent was concentrated,The silica gel column chromatography was used for separation and purification to obtain 74 parts of the compound represented by formula (a-3).
	With 1H-imidazole In dichloromethane at 20℃; for 15h;	7-9 (3-Bromophenoxy)(tert-butyl)dimethylsilane (32) 3-Bromophenol 22 (2.08 g, 12 mmol) was taken in dry DCM (40 mL, 0.3 M). This was charged with TBDMS-Cl (2.0 g, 13 mmol). This was then charged with imidazole (1.37 g, 20 mmol) and allowed to stir at room temperature for next 15 hours. The reaction mass was directly filtered off and residue washed with DCM. The filtrate was concentrated and crude obtained was purified over silica gel column chromatography (0-5% EA:hexanes) to get the pure product. 1H-NMR (300 MHz, CDCl3) δ 0.20 (s, 6H), 0.97 (s, 9H), 6.74-6.78 (m, 1H), 7.00 (s, 1H), 7.07-7.09 (m, 1H).

Reference： [1]Boswell; McNutt; Bubacz; Davis; Chang [Journal of Heterocyclic Chemistry, 1995, vol. 32, # 6, p. 1801 - 1818]
[2]Location in patent: experimental part Iqbal, Zafar; Lyubimtsev, Alexey; Hanack, Michael [Synlett, 2008, # 15, p. 2287 - 2290]
[3]Location in patent: experimental part Hille, Ulrike E.; Hu, Qingzhong; Vock, Carsten; Negri, Matthias; Bartels, Marc; Mueller-Vieira, Ursula; Lauterbach, Thomas; Hartmann, Rolf W. [European Journal of Medicinal Chemistry, 2009, vol. 44, # 7, p. 2765 - 2775]
[4]Current Patent Assignee: AMOREPACIFIC CORP. - WO2010/2209, 2010, A2 Location in patent: Page/Page column 88
[5]Misra; Brown; Han; Harris; Hedberg; Webb; Hall [Journal of Medicinal Chemistry, 1991, vol. 34, # 9, p. 2882 - 2891]
[6]Current Patent Assignee: Valline SRL - US2016/235734, 2016, A1 Location in patent: Paragraph 0416; 0417; 0418
[7]Reid, William B.; Watson, Donald A. [Organic Letters, 2018, vol. 20, # 21, p. 6832 - 6835]
[8]Current Patent Assignee: VERSI GROUP - WO2007/27987, 2007, A2 Location in patent: Page/Page column 15-16
[9]Current Patent Assignee: VERSI GROUP - WO2017/173067, 2017, A1 Location in patent: Page/Page column 19; 20
[10]Current Patent Assignee: VERSI GROUP - WO2018/204163, 2018, A1 Location in patent: Paragraph 0078; 0080
[11]Current Patent Assignee: BAYLOR UNIVERSITY - WO2017/30983, 2017, A1 Location in patent: Paragraph 0153; 0154; 0155
[12]Parker, Erica N.; Odutola, Samuel O.; Wang, Yifan; Strecker, Tracy E.; Mukherjee, Rajeswari; Shi, Zhe; Chaplin, David J.; Trawick, Mary Lynn; Pinney, Kevin G. [Bioorganic and Medicinal Chemistry Letters, 2017, vol. 27, # 5, p. 1304 - 1310]
[13]Chan, Jefferson; Ibarra, Gabriela E.; Krishnamurthy, Vishnu; Pino, Nicholas W.; Smaga, Lukas P. [Journal of the American Chemical Society, 2020]
[14]He, Zhen; Shrives, Harry J.; Fernández-Salas, José A.; Abengózar, Alberto; Neufeld, Jessica; Yang, Kevin; Pulis, Alexander P.; Procter, David J. [Angewandte Chemie - International Edition, 2018, vol. 57, # 20, p. 5759 - 5764][Angew. Chem., 2018, vol. 57, # 130, p. 5861 - 5866,6]
[15]Current Patent Assignee: NEKTAR THERAPEUTICS - US2015/335640, 2015, A1 Location in patent: Paragraph 0304
[16]Current Patent Assignee: UNIVERSITY OF ILLINOIS (SYSTEM) - US2020/199092, 2020, A1 Location in patent: Paragraph 0247
[17]Bastos, Erick L.; Ciscato, Luiz F. M. L.; Baader, Wilhelm J. [Synthetic Communications, 2005, vol. 35, # 11, p. 1501 - 1509]
[18]Martinelli, Michael J.; Peterson, Barry C.; Hutchison, Darrell R. [Heterocycles, 1993, vol. 36, # 9, p. 2087 - 2098]
[19]Bosse, Folkert; Tunoori, Ashok Rao; Maier, Martin E. [Tetrahedron, 1997, vol. 53, # 27, p. 9159 - 9168]
[20]Ikuma, Naohiko; Tsue, Hirohito; Tsue, Naoko; Shimono, Satoshi; Uchida, Yoshiaki; Masaki, Kazuyoshi; Matsuoka, Nagahisa; Tamura, Rui [Organic Letters, 2005, vol. 7, # 9, p. 1797 - 1800]
[21]Bishop, Michael J.; Garrido, Dulce M.; Boswell, G. Evan; Collins, Mark A.; Harris, Philip A.; McNutt, Robert W.; O'Neill, Scott J.; Wei, Ke; Chang, Kwen-Jen [Journal of Medicinal Chemistry, 2003, vol. 46, # 4, p. 623 - 633]
[22]Current Patent Assignee: SOSEI GROUP CORPORATION - WO2005/103019, 2005, A1 Location in patent: Page/Page column 21
[23]Current Patent Assignee: Dongwoo Fine-Chem (in: Sumitomo Chemical); SUMITOMO CHEMICAL COMPANY LIMITED - JP2020/55956, 2020, A Location in patent: Paragraph 0177-0179
[24]Current Patent Assignee: SUMITOMO CHEMICAL COMPANY LIMITED; Sumitomo Chemical (w/o Dongwoo Fine-Chem) - TW2020/39699, 2020, A Location in patent: Paragraph 0155-0157
[25]Current Patent Assignee: KOREA RESEARCH INSTITUTE OF CHEMICAL TECHNOLOGY - US2021/322362, 2021, A1 Location in patent: Paragraph 0267-0268

2
[ 65423-56-5 ]
methyl 3-bromobicyclo[2.2.2]octa-2,5-diene-2-carboxylate [ No CAS ]
methyl 3-[3-(tert-butyldimethylsilyloxy)phenyl]bicyclo[2.2.2]octa-2,5-diene-2-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
40%	Stage #1: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.25h; Stage #2: With zinc dibromide In tetrahydrofuran; hexane at 0℃; for 0.0833333h; Stage #3: methyl 3-bromobicyclo[2.2.2]octa-2,5-diene-2-carboxylate With triphenylphosphine In tetrahydrofuran; hexane at -78 - 20℃; for 15h;

Reference： [1]Bosse, Folkert; Maier, Martin E. [Advanced Synthesis and Catalysis, 2000, vol. 342, # 1, p. 6 - 9]

3
[ 121-43-7 ]
[ 65423-56-5 ]
[ 261621-12-9 ]

Reference： [1]Advanced Synthesis and Catalysis,2000,vol. 342,p. 6 - 9

4
[ 65423-56-5 ]
[ 178379-39-0 ]
[ 392235-12-0 ]

Yield	Reaction Conditions	Operation in experiment
61%	Stage #1: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With tert.-butyl lithium In diethyl ether; pentane at -78 - 0℃; for 1.33333h; Stage #2: (1S,3aS,7aR)-1-hydroxymethyl-3a-hydroxy-7a-methyl-5-perhydroindenone In tetrahydrofuran; diethyl ether; pentane at -78℃; for 0.5h; Further stages.;

Reference： [1]Cerri; Almirante; Barassi; Benicchio; De Munari; Marazzi; Molinari; Serra; Melloni [Journal of Medicinal Chemistry, 2002, vol. 45, # 1, p. 189 - 207]

5
[ 3132-99-8 ]
[ 65423-56-5 ]
[ 155767-23-0 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 2h; Stage #2: m-bromobenzoic aldehyde In tetrahydrofuran; hexane at -78℃; for 2h; Further stages.;
	Stage #1: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With n-butyllithium In tetrahydrofuran at -78℃; Stage #2: m-bromobenzoic aldehyde In tetrahydrofuran

Reference： [1]Bishop, Michael J.; Garrido, Dulce M.; Boswell, G. Evan; Collins, Mark A.; Harris, Philip A.; McNutt, Robert W.; O'Neill, Scott J.; Wei, Ke; Chang, Kwen-Jen [Journal of Medicinal Chemistry, 2003, vol. 46, # 4, p. 623 - 633]
[2]Current Patent Assignee: BAYLOR UNIVERSITY - WO2017/30983, 2017, A1 Location in patent: Paragraph 0160

6
[ 65423-56-5 ]
tetrakis(3,5-bis{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}benzyl) 4,4',4",4"'-[10-(2-ethynylphenyl)porphyrin-5,15-diyl]bis[benzene-2,1,3-triylbis(oxy)]butanoate [ No CAS ]
C₁₅₂H₂₀₄N₄O₄₅Si [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine In 1,2-dichloro-benzene at 120℃; for 6h;

Reference： [1]Felber, Beatrice; Calle, Carlos; Seiler, Paul; Schweiger, Arthur; Diederich, Francois [Organic and biomolecular chemistry, 2003, vol. 1, # 7, p. 1090 - 1093]

7
[ 65423-56-5 ]
[ 627461-21-6 ]
[ 627461-20-5 ]

Yield	Reaction Conditions	Operation in experiment
53%	With triethylamine In N,N-dimethyl-formamide at 80℃;

Reference： [1]Perez-Garcia, Xenxo; Rumbo, Antonio; Larriba, Maria Jesus; Ordonez, Paloma; Munoz, Alberto; Mourino, Antonio [Organic Letters, 2003, vol. 5, # 22, p. 4033 - 4036]

8
[ 930-68-7 ]
[ 65423-56-5 ]
1-[3-(tert-butyldimethylsilanyloxy)phenyl]-2-cyclohexen-1-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With tert.-butyl lithium In tetrahydrofuran; pentane at -78℃; Stage #2: cyclohexenone In tetrahydrofuran; pentane at -78℃; for 1h;

Reference： [1]Shibuya, Masatoshi; Ito, Shinichiro; Takahashi, Michiyasu; Iwabuchi, Yoshiharu [Organic Letters, 2004, vol. 6, # 23, p. 4303 - 4306]

9
diisopropylcarbamic acid (S)-(+)-1-(4,4,5,5-tetramethyl[1,3,2]dioxaborolan-2-yl)-3-(3,4,5-trimethoxyphenyl)propyl ester [ No CAS ]
[ 65423-56-5 ]
C₃₀H₄₇BO₆Si [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With magnesium; ethylene dibromide In diethyl ether for 4h; Heating; Stage #2: diisopropylcarbamic acid (S)-(+)-1-(4,4,5,5-tetramethyl[1,3,2]dioxaborolan-2-yl)-3-(3,4,5-trimethoxyphenyl)propyl ester In diethyl ether at 20℃; for 12h; Further stages.;

Reference： [1]Besong, Gilbert; Jarowicki, Krzysztof; Kocienski, Philip J.; Sliwinski, Eric; Boyle, F. Thomas [Organic and Biomolecular Chemistry, 2006, vol. 4, # 11, p. 2193 - 2207]

10
[ 65423-56-5 ]
[ 627461-26-1 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1.1: 53 percent / Et₃N / PdCl₂(PPh₃)2 / dimethylformamide / 80 °C 2.1: HF / 2 h / 20 °C 2.2: 70 percent / pyridinium dichromate / CH₂Cl₂ / 4 h / 20 °C

Reference： [1]Perez-Garcia, Xenxo; Rumbo, Antonio; Larriba, Maria Jesus; Ordonez, Paloma; Munoz, Alberto; Mourino, Antonio [Organic Letters, 2003, vol. 5, # 22, p. 4033 - 4036]

11
[ 65423-56-5 ]
(1R,3S)-5-[2-[(1S,3aS,7aS)-1-(3-Hydroxy-phenylethynyl)-7a-methyl-octahydro-inden-(4E)-ylidene]-eth-(Z)-ylidene]-4-methylene-cyclohexane-1,3-diol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 4 steps 1.1: 53 percent / Et₃N / PdCl₂(PPh₃)2 / dimethylformamide / 80 °C 2.1: HF / 2 h / 20 °C 2.2: 70 percent / pyridinium dichromate / CH₂Cl₂ / 4 h / 20 °C 3.1: 75 percent / n-BuLi / hexane; tetrahydrofuran / -78 - -40 °C 4.1: 79 percent / nBu₄NF / tetrahydrofuran / 20 °C

Reference： [1]Perez-Garcia, Xenxo; Rumbo, Antonio; Larriba, Maria Jesus; Ordonez, Paloma; Munoz, Alberto; Mourino, Antonio [Organic Letters, 2003, vol. 5, # 22, p. 4033 - 4036]

12
[ 65423-56-5 ]
[ 627461-27-2 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1.1: 53 percent / Et₃N / PdCl₂(PPh₃)2 / dimethylformamide / 80 °C 2.1: HF / 2 h / 20 °C 2.2: 70 percent / pyridinium dichromate / CH₂Cl₂ / 4 h / 20 °C 3.1: 75 percent / n-BuLi / hexane; tetrahydrofuran / -78 - -40 °C

Reference： [1]Perez-Garcia, Xenxo; Rumbo, Antonio; Larriba, Maria Jesus; Ordonez, Paloma; Munoz, Alberto; Mourino, Antonio [Organic Letters, 2003, vol. 5, # 22, p. 4033 - 4036]

13
[ 65423-56-5 ]
methyl 3-[3-(tert-butyldimethylsilyloxy)phenyl]bicyclo[2.2.2]octa-2,5-diene-2-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1.1: 1.6 M nBuLi / tetrahydrofuran; hexane / 0.25 h / -78 °C 1.2: tetrahydrofuran; hexane / 6.5 h / -78 - 20 °C 1.3: 51 percent / sat. NH₄Cl / tetrahydrofuran; hexane / 0.08 h / 0 °C 2.1: 45 percent / Ph₃As; aq. Na₂CO₃ / Pd₂(dba)3*CHCl₃ / dioxane / 1.5 h / Heating

Reference： [1]Bosse, Folkert; Maier, Martin E. [Advanced Synthesis and Catalysis, 2000, vol. 342, # 1, p. 6 - 9]

14
[ 65423-56-5 ]
7-[3-(tert-butyldimethylsilyloxy)phenyl]-6-hydroxymethyl-1,3,3a,4,5,6-hexahydro-1-isobenzofuranone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1.1: 1.6 M nBuLi / tetrahydrofuran; hexane / 0.25 h / -78 °C 1.2: tetrahydrofuran; hexane / 6.5 h / -78 - 20 °C 1.3: 51 percent / sat. NH₄Cl / tetrahydrofuran; hexane / 0.08 h / 0 °C 2.1: 45 percent / Ph₃As; aq. Na₂CO₃ / Pd₂(dba)3*CHCl₃ / dioxane / 1.5 h / Heating 3.1: O₃; sudan III; pyridine / ethanol; CH₂Cl₂; methanol / -78 °C 3.2: NaBH₄; pyridine / ethanol; CH₂Cl₂; methanol / 14 h / -78 - 20 °C 3.3: 43 percent / aq. HCl; pyridine / ethanol; CH₂Cl₂; methanol

Reference： [1]Bosse, Folkert; Maier, Martin E. [Advanced Synthesis and Catalysis, 2000, vol. 342, # 1, p. 6 - 9]

15
[ 65423-56-5 ]
methyl 3-[3-(tert-butyldimethylsilyloxy)phenyl]-5,6-dihydroxy-bicyclo[2.2.2]oct-2-ene-2-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1.1: 1.6 M nBuLi / tetrahydrofuran; hexane / 0.25 h / -78 °C 1.2: tetrahydrofuran; hexane / 6.5 h / -78 - 20 °C 1.3: 51 percent / sat. NH₄Cl / tetrahydrofuran; hexane / 0.08 h / 0 °C 2.1: 45 percent / Ph₃As; aq. Na₂CO₃ / Pd₂(dba)3*CHCl₃ / dioxane / 1.5 h / Heating 3.1: 37 percent / OsO₄; tBuOOH / acetone; H₂O; 2-methyl-propan-2-ol / 21.75 h / 0 - 20 °C

Reference： [1]Bosse, Folkert; Maier, Martin E. [Advanced Synthesis and Catalysis, 2000, vol. 342, # 1, p. 6 - 9]

16
[ 65423-56-5 ]
[ 127898-35-5 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: 1.) tert-butyllithium / 1.) ether, pentane, a) -78 deg C, 30 min, b) 0 deg C, 15 min, 2.) ether, pentane, THF, 0 deg C, 1 h 2: 70 percent / H₂, glacial CH₃COOH / 10percent Pd/C / 40 h / 2068.6 Torr 3: 98 percent / 48percent aq. HF / acetonitrile / 4 h / 25 °C

Reference： [1]Misra; Brown; Han; Harris; Hedberg; Webb; Hall [Journal of Medicinal Chemistry, 1991, vol. 34, # 9, p. 2882 - 2891]

17
[ 65423-56-5 ]
[ 127898-37-7 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 5 steps 1: 1.) tert-butyllithium / 1.) ether, pentane, a) -78 deg C, 30 min, b) 0 deg C, 15 min, 2.) ether, pentane, THF, 0 deg C, 1 h 2: 70 percent / H₂, glacial CH₃COOH / 10percent Pd/C / 40 h / 2068.6 Torr 3: 98 percent / 48percent aq. HF / acetonitrile / 4 h / 25 °C 4: 1.) NaH / 1.) THF, 25 deg C, 1 h, 2.) THF, DMF, 2 h 5: Dess-Martin periodinane / CH₂Cl₂ / 0.25 h / 25 °C

Reference： [1]Misra; Brown; Han; Harris; Hedberg; Webb; Hall [Journal of Medicinal Chemistry, 1991, vol. 34, # 9, p. 2882 - 2891]

18
[ 65423-56-5 ]
[ 127898-36-6 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 4 steps 1: 1.) tert-butyllithium / 1.) ether, pentane, a) -78 deg C, 30 min, b) 0 deg C, 15 min, 2.) ether, pentane, THF, 0 deg C, 1 h 2: 70 percent / H₂, glacial CH₃COOH / 10percent Pd/C / 40 h / 2068.6 Torr 3: 98 percent / 48percent aq. HF / acetonitrile / 4 h / 25 °C 4: 1.) NaH / 1.) THF, 25 deg C, 1 h, 2.) THF, DMF, 2 h

Reference： [1]Misra; Brown; Han; Harris; Hedberg; Webb; Hall [Journal of Medicinal Chemistry, 1991, vol. 34, # 9, p. 2882 - 2891]

19
[ 65423-56-5 ]
<1S-1α,2α,3α,4α>-<2-<<3-<<<(phenylamino)carbonyl>hydrazono>methyl>-7-oxabicyclo<2.2.1>hept-2-yl>methyl>phenoxy>acetic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 7 steps 1: 1.) tert-butyllithium / 1.) ether, pentane, a) -78 deg C, 30 min, b) 0 deg C, 15 min, 2.) ether, pentane, THF, 0 deg C, 1 h 2: 70 percent / H₂, glacial CH₃COOH / 10percent Pd/C / 40 h / 2068.6 Torr 3: 98 percent / 48percent aq. HF / acetonitrile / 4 h / 25 °C 4: 1.) NaH / 1.) THF, 25 deg C, 1 h, 2.) THF, DMF, 2 h 5: Dess-Martin periodinane / CH₂Cl₂ / 0.25 h / 25 °C 6: methanol / 40 h / 25 °C 7: LiOH*H₂O / tetrahydrofuran; H₂O / 3 h / 25 °C

Reference： [1]Misra; Brown; Han; Harris; Hedberg; Webb; Hall [Journal of Medicinal Chemistry, 1991, vol. 34, # 9, p. 2882 - 2891]

20
[ 65423-56-5 ]
C₂₅H₂₉N₃O₅ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 6 steps 1: 1.) tert-butyllithium / 1.) ether, pentane, a) -78 deg C, 30 min, b) 0 deg C, 15 min, 2.) ether, pentane, THF, 0 deg C, 1 h 2: 70 percent / H₂, glacial CH₃COOH / 10percent Pd/C / 40 h / 2068.6 Torr 3: 98 percent / 48percent aq. HF / acetonitrile / 4 h / 25 °C 4: 1.) NaH / 1.) THF, 25 deg C, 1 h, 2.) THF, DMF, 2 h 5: Dess-Martin periodinane / CH₂Cl₂ / 0.25 h / 25 °C 6: methanol / 40 h / 25 °C

Reference： [1]Misra; Brown; Han; Harris; Hedberg; Webb; Hall [Journal of Medicinal Chemistry, 1991, vol. 34, # 9, p. 2882 - 2891]

21
[ 571903-29-2 ]
[ 65423-56-5 ]
[ 571903-33-8 ]

Yield	Reaction Conditions	Operation in experiment
80%		3.a a) 7-(3-t-butyidimethysilyloxyphenylsulfonyl)-2,3,4,5-tetrahydro-1H-3-benzazepine Prepared from 3-trifluoroacetyl-8-methoxy-2, 3,4, [5-TETRAHYDRO-1H-3-BENZAZEPINE-7-SULFONYL] chloride using the method of Description 1 (b), yield 80%.

Reference： [1]Current Patent Assignee: GLAXOSMITHKLINE PLC - WO2003/99786, 2003, A2 Location in patent: Page 28

22
[ 65423-56-5 ]
[ 133776-41-7 ]
[ 886574-92-1 ]

Yield	Reaction Conditions	Operation in experiment
	With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.333333h;	8; C.c Reference example 8: (2-Aminophenyl)(3'-tert-butyldimethylsilyloxyphenyl)methanone. Method: General procedure C c) Starting compound: 2-Amino-N-methoxy-N-methylbenzamide (reference example 1) Reactant: (3-Bromophenoxy)(tert-butyl)dimethylsilane 1H NMR (200 MHz, CDCl3): δ (ppm) = 0.22 (6H, s), 0.99 (9H, s), 6.11 (2H, brs), 6.57-6.65 (1 H, m), 6.74 (1H, d, J= 8.4), 7.01 (1 H, m), 7.10 (1 H, m), 7.19-7.36 (3H, m), 7.47 (1 H, dd, J=1.5, 8.1 Hz) 13C NMR (50 MHz,: CDCl3): δ (ppm) = -4.2, 18.4, 25.8, 115.6, 117.1, 118.3, 120.7, 122.3, 123.0, 129.3, 134.4, 134.8, 141.6, 151.1, 155.5, 198.9; ESI-HRMS m/z: calcd for C19H26NO2Si (MH+) 328.17273, found 328.17280; oil.; General procedure C c) 2-Aminobenzophenones of the formula (IX). 2-Aminobenzophenones of the formula (IX) were prepared from the corresponding N-methoxy-N-methylamides according to S. V. Frye, M. C. Johnson, N. L. Valvano, J. Org. Chem. 1991, 56, 3750-3752. This synthesis is outlined in the following scheme 8: [Show Image] Briefly, to a mixture of the appropriate N-methoxy-N-methylamide (compound of formula (VIII), 11.1 mmol) and the appropriate (hetero)arylbromide (compound of the formula R1a-Br; 11.1 mmol) in anhydrous tetrahydrofuran (65 mL) at -78 °C under nitrogen was added, with vigorous stirring, n-BuLi in hexanes (13.8 mL, 1.6 M, 22.2 mmol) at 0.6 mL/min. After 20 min, aqueous hydrochloric acid was added (1 N, 20 mL), the mixture was extracted with ethyl acetate (150 mL), and the ethyl acetate was washed with water and brine, dried over magnesium sulfate, and concentrated. If an oil was obtained, this was chromatographed on silica gel (hexane / ethyl acetate, 1:1) to afford the product.

Reference： [1]Current Patent Assignee: EUROPEAN MOLECULAR BIOLOGY LABORATORY; MAX-PLANCK-GESELLSCHAFT ZUR FÖRDERUNG DER WISSENSCHAFT E.V.; LEIPZIG UNIVERSITY - EP1655289, 2006, A1 Location in patent: Page/Page column 17; 19

23
[ 288-32-4 ]
[ 591-20-8 ]
[ 18162-48-6 ]
[ 65423-56-5 ]

Yield	Reaction Conditions	Operation in experiment
	In dichloromethane	(3-Bromophenoxy)-(tert-butyl)-dimethylsilane (3-Bromophenoxy)-(tert-butyl)-dimethylsilane A suspension of 3-bromo-phenol (5.5 g, 31.8 mmoles), imidazole (4.3 g, 63.6 mmoles) in CH2Cl2 (70 ml) was added dropwise to a solution of tert-butyl-chloro-dimethylsilane (5.3 g, 35 mmoles) in CH2Cl2 (5 ml) at 0° C. The reaction mixture was stirred for 3 hours at room temperature then evaporated to dryness under vacuum. The residue was partitioned between water and ethyl acetate and from the organic solution after essiccation over MgSO4, filtration and evaporation the title compound was obtained. 7.5 g, yellow oil 1H-NMR (CDCl3; 200 MHz) 7.05-7.11 (ov, 2H); 7.00 (m, 1H); 6.76 (m, 1 H); 0.97 (s, 9H): 0.20 (s, 6H)

Reference： [1]Current Patent Assignee: C.H. Boehringer Sohn AG & Co. KG - US2002/120072, 2002, A1

24
chloro-tert-butyl-dimethylsilane [ No CAS ]
[ 65423-56-5 ]

Yield	Reaction Conditions	Operation in experiment
18.8 g (65.5 mmol, 99%)	With hydrogenchloride In <i>N</i>-methyl-acetamide; hexane	1.A A. A. (3-Bromophenoxy) (1,1-dimethylethyl)dimethylsilane A solution of 11.5 g (66.5 mmol, Aldrich) of m-bromophenol, 6.80 g (100 mmol, Aldrich) of imidazole and 10.3 g (68.3 mmol, Aldrich) of chloro-t-butyldimethylsilane in 75 mL of sieve-dried dimethylformamide was stirred at room temperature for 18 hours. The reaction mixture was then partitioned between 250 mL of cold 1M aqueous HCl solution and 150 mL of hexane. The organic layer was separated and the aqueous layer extracted with an additional 100 mL of hexane. The organic extracts were combined, washed with 100 mL of saturated aqueous sodium bicarbonate solution, then 100 mL of water, dried (magnesium sulfate) and concentrated in vacuo to afford 18.8 g (65.5 mmol, 99%) of title compound as a colorless oil.

Reference： [1]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - US4883809, 1989, A

25
[ 288-32-4 ]
B-dichloromethane [ No CAS ]
[ 591-20-8 ]
[ 18162-48-6 ]
[ 65423-56-5 ]

Yield	Reaction Conditions	Operation in experiment
	In <i>N</i>-methyl-acetamide	2.I 3-(tert-Butyldimethylsilyloxy)-phenylithium Cuprate Reactant I. There is first prepared 1-bromo-3-(tert-butyldimethylsilyloxy)benzene: STR44 A solution of m-bromophenol (10.0 g.) in 40 ml. of dimethylformamide is treated with t-butyldimethylchlorosilane (17.42 g.) and imidazole (15.74 g.) at 23° C. for 16 hr. The mixture is diluted with brine and extracted with Skellysolve B-dichloromethane (3:1). The extracts are washed with brine, dried over sodium sulfate, and concentrated to an oil, 29.07 g. The oil is distilled to give the desired 1-bromo-3-(tert-butyldimethylsilyloxy)benzene, 13.47 g., b.p. 66° C. (0.28 mm.).
	In <i>N</i>-methyl-acetamide	2.1 3-(tert-Butyldimethylsilyloxy)-phenyl-lithium Cuprate Reactant 1. There is first prepared 1-bromo-3-(tert-butyldimethylsilyloxy)benzene: STR39 A solution of m-bromophenol (10.0 g.) in 40 ml. of dimethylformamide is treated with t-butyldimethylchlorosilane (17.42 g.) and imidazole (15.74 g.) at 23° C. for 16 hr. The mixture is diluted with brine and extracted with Skellysolve B-dichloromethane (3:1). The extracts are washed with brine, dried over sodium sulfate, and concentrated to an oil, 29.07 g. The oil is distilled to give the desired 1-bromo-3-(tert-butyldimethylsilyloxy)-benzene, 13.47 g., b.p. 66° C. (0.28 mm.).

Reference： [1]Current Patent Assignee: PFIZER INC - US4100192, 1978, A
[2]Current Patent Assignee: PFIZER INC - US4181798, 1980, A

26
[ 199938-28-8 ]
[ 65423-56-5 ]
ammonium chloride [ No CAS ]
[ 117973-14-5 ]
[ 199938-29-9 ]

Yield	Reaction Conditions	Operation in experiment
49%	With magnesium In tetrahydrofuran; diethyl ether	263.3 Example 263 3. A solution of 3-(tert-butyldimethylsilyloxy)phenylmagnesium bromide [prepared from 3-(tert-butyldimethylsilyloxy)bromobenzene (28.5 g, 99.2 mmol) and magnesium turnings (2.30 g, 94.5 mmol) in Et2O (65 mL) ] was added at 0 _C to a solution of the purified 1-(tert-Butyloxycarbonyl)-4-(3-phenyl-3-oxopropyl)homopiperazine (11.25 g, 33.8 mmol) in dry THF (150 mL). The mixture was warmed to room temperature with stirring and the stirring was continued for 3 h. Saturated aqueous NH4Cl (300 mL) was added to the reaction mixture, the mixture was stirred for 15 min and extracted with AcOEt (3 x 150 mL). The combined extracts were washed with brine and dried over MgSO4. The solvent was removed under reduced pressure to afford an oil (31.00 g) which was purified by column chromatography (SiO2, 3%-25% AcOEt/hexane) to give 1-(tert-butyloxycarbonyl)-4-[3-{3-(tert-butyldimethylsilyloxy)phenyl}-3-hydroxy-3-phenylpropyl]homopiperazine: 9.00 g, 49% yield, pale yellow oil; 1H NMR (CDCl3, 300 MHz) δ 0.00 (s. 6 H), 0.81 (s, 9 H), 1.32 (s, 9 H), 1.4-1.5 (m. 2 H), 1.7-1.8 (m, 2 H), 2.2-2.3 (m, 2 H), 2.4-2.55 (m, 4 H), 3.25-3.45 (m. 4 H), 6.50-6.56 (m, 1 H). 6.80-6.92 (m, 2 H), 6.99-7.10 (m. 2 H), 7.11-7.20 (m, 2 H), 7.28-7.34 (m, 2 H). The purity was determined by RPLC/MS (Method A). RPLC tR = 7.13 min (>95%), 220 nm; ESI/MS m/e 541.3 (M+H, C31H49N2O2Si).

Reference： [1]Current Patent Assignee: TEIJIN LIMITED - EP914319, 2001, B1

27
[ 65423-56-5 ]
[ 117973-14-5 ]

Yield	Reaction Conditions	Operation in experiment
	With magnesium In tetrahydrofuran for 1h; Heating / reflux;	1.A 3-tert-Butyldimethylsilyloxyphenylmagnesium bromide was formed by the slow addition of a mixture of 3-bromophenoxy-tert-butyldimethylsilane (27.3 g, 92.6 mmol) and dibromoethane (3.45 g, 18.4 mmol) in inhibitor-free anhydrous tetrahydrofuran (100 mL) to a solution of magnesium turnings (3.57 g, 147 mmol) in inhibitor-free anhydrous tetrahydrofuran (200 mL) at reflux. After stirring for one hour at reflux the light brown clear mixture was cooled to room temperature.
	With magnesium; ethylene dibromide In tetrahydrofuran for 1h; Reflux;	1.A Method A - Alkylation with phenol protection 3-tert-Butyldimethylsilyloxyphenylmagnesium bromide was formed by the slow addition of a mixture of 3-bromophenoxy-tert-butyldimethylsilane (27.3 g, 92.6 mmol) and dibromoethane (3.45 g, 18.4 mmol) in inhibitor-free anhydrous tetrahydrofuran (100 mL) to a solution of10 magnesium turnings (3.57 g, 147 mmol) in inhibitor-free anhydrous tetrahydrofuran (200 mL) at reflux. After stirring for one hour at reflux the light brown clear mixture was cooled to room temperature.
	With magnesium; ethylene dibromide In tetrahydrofuran for 1h; Reflux;	1 3-tert-Butyldimethylsilyloxyphenylmagnesium bromide was formed by the slowaddition of a mixture 3-bromophenoxy-tert-butyldimethylsilane (118g, 400 mmol) and dibromoethane (1 5g, 80 mmol) in 400 mL of inhibitor-free anhydrous tetrahydrofuran to a solution of magnesium turnings (15.5g, 640 mmol) in 800 mL of inhibitor-free anhydrous tetrahydrofuran at reflux. After stirring for one hour at reflux the light brown clear mixture was cooled to room temperature.

Reference： [1]Current Patent Assignee: VERSI GROUP - WO2007/27987, 2007, A2 Location in patent: Page/Page column 16
[2]Current Patent Assignee: VERSI GROUP - WO2017/173067, 2017, A1 Location in patent: Page/Page column 20
[3]Current Patent Assignee: VERSI GROUP - WO2018/204163, 2018, A1 Location in patent: Paragraph 0078; 0081

28
[ 108-77-0 ]
[ 65423-56-5 ]
[ 1033594-08-9 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With magnesium In tetrahydrofuran at 20℃; for 2h; Heating / reflux; Stage #2: 1,3,5-trichloro-2,4,6-triazine In tetrahydrofuran at 0 - 20℃; for 3h;	III-1.1 Example III-l: 3-[4-(Hexahydropyrrolo[l,2,«]pyrazin-2-yl)-6-((3i?)- hydroxymethyl-S^-dihydro-li-isoquinolin^-y^-tl^^ltriazin-l-yll-phenolStep 1) 3-[4-Chloro-6-((3R)-hydroxymethyl-3,4-dihydro-lH-isoquinolin-2-yl)- [ 1 ,3 ,5]triazin-2-yl]-phenol (3-Bromophenoxy)-tert-butyldimethylsilane (14 g, 48.7 mmol) dissolved in tetrahydrofuran (30 ml) was added dropwise at room temperature to a mixture of magnesium (3.6 g, 146 mmol), iodine (catalytic amount) and tetrahydrofuran (2 ml), and refluxed for 2 hour followed by cooling to room temperature. The resulting mixture was added dropwise at 0°C to 2,4,6- trichloro-[l,3,5]triazine (8.99 g, 48.7 mmol) dissolved in tetrahydrofuran (20 ml), and stirred at room temperature for 3 hours. Then, the resulting solution was added to aqueous ammonium chloride, and extracted twice with diethyl ether. The separated organic layer was washed successively with water and saturated NaCl, dried over anhydrous magnesium sulfate, and concentrated under a reduced pressure. The resulting residue was purified by column chromatography to obtain 2-[3-(tert-butyldimethylsilanyloxy)-phenyl]-4,6- dichloro-[l,3,5]triazine (5.3g).

Reference： [1]Current Patent Assignee: CRYSTAL GENOMICS INC.; AMOREPACIFIC CORP.; GYEONGSANG NATIONAL UNIVERSITY - WO2008/72850, 2008, A1 Location in patent: Page/Page column 40-41

29
[ 108-30-5 ]
[ 65423-56-5 ]
[ 850664-15-2 ]

Yield	Reaction Conditions	Operation in experiment
54%	Stage #1: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With n-butyllithium In tetrahydrofuran; hexanes at -78℃; for 0.333333h; Stage #2: succinic acid anhydride In tetrahydrofuran; hexanes at -78 - 20℃;	20.1 Step 1. 4-(3-[(1,1-dimethylethyl) (dimethyl) silyl]oxy} phenyl) -4-oxobutanoic acid Under argon, to a solution of [ (3-bromophenyl) oxy] (1, 1-dimethylethyl)- dimethylsilane (1.5 g, 5.22 mmol) in THF (60 mL) at-78 °C, was added dropwise n- BuLi (3.6 mL, 1.6 M in hexanes), 20 min after the addition, this solution was added to a solution of dihydro-2, 5-furandione (630 mg, 6.26 mmol) in THF (10 mL) under argon at-78 °C. 15 min later, the reaction mixture was slowly warmed to rt overnight. The reaction mixture was diluted with EtOAc (50 mL), then extracted with NaOH (20ml, 1.0 N). Aquaous layer was acidified with HCl (1. ON) until pH = 2, then extracted with EtOAc (100 mL). The organic layer was washed with brine, dried over Na2S04, filtered and concentrated to afford the title compound as a colorless crystal (546 mg, 54%).

Reference： [1]Current Patent Assignee: GLAXOSMITHKLINE PLC - WO2005/37197, 2005, A2 Location in patent: Page/Page column 110

30
[ 136386-79-3 ]
[ 1123-89-3 ]
[ 1089178-86-8 ]
[ 65423-56-5 ]

Yield	Reaction Conditions	Operation in experiment
1: 93.7% 2: 3%	Stage #1: (3,5-dibromophenoxy)-tert-butyldimethylsilane With isopropylmagnesium chloride In tetrahydrofuran at 20 - 65℃; Stage #2: 2-Methyl-phenylcyanat In tetrahydrofuran; n-heptane at 10℃;	11.1 A degassed reactor was charged with a THF solution of iso-PrMgCl (1.14 equiv., 2M solution in THF) and B-1a (495.2 g, 1.352 mol; CASRN 136386-79-3) was pumped into the reactor while the temperature below 65° C. with a water bath. After the exothermicity subsided, the reaction was stirred at RT until metallation was complete (Aliquots removed, quenched with dil. H2SO4 and assayed by gas chromatography). The resulting solution containing the aryl Grignard reagent was added to a heptane solution of cresol cyanate (supra; CASRN 1123-89-3) while maintaining the reaction temperature below 10° C. The reaction was monitored by removing aliquots, quenching with dilute and H2SO4 and assaying the cresol/cyanate ratio. When the cyanate was consumer the reaction mixture was added to a dilute H2SO4 solution (86.5 g H2SO4 and 2.15 L H2O). The aqueous layer was separated and the remaining organic phase was diluted with heptane and washed sequentially with ice cold aqueous NaOH (320 g of 50% NaOH and 1 kg of ice), water, saturated NH4Cl and water. The solution was dried by azeotropic distillation and the product was purified by vacuum distillation to afford 395.7 g (93.7%) B-1b contaminated with 3-6% 3-(tert-butyl-dimethylsilyloxy)-bromobenzene.
93.7%	Stage #1: (3,5-dibromophenoxy)-tert-butyldimethylsilane With isopropylmagnesium chloride In tetrahydrofuran at 20 - 65℃; Stage #2: 2-Methyl-phenylcyanat In tetrahydrofuran; n-heptane at 10℃;	6.1 A degassed reactor was charged with a THF solution of zso-PrMgCl (1.14 equiv., 2M solution in THF) and 11a (495.2 g, 1.352 mol; CASRN 136386-79-3) was pumped into the reactor while the temperature below 65° C with a water bath. After the exothermicity subsided, the reaction was stirred at RT until metallation was complete (Aliquots removed, quenched with dil. H2SO4 and assayed by gas chromatography). The resulting solution containing the aryl Grignard reagent was added to a heptane solution of cresol cyanate (supra; CASRN 1123-89-3) while maintaining the reaction temperature below 10° C. The reaction was monitored by removing aliquots, quenching with dilute and H2SO4 and assaying the cresol/cyanate ratio. When the cyanate was consumer the reaction mixture was added to a dilute H2SO4 solution (86.5 g H2SO4 and 2.15 L H2O). The aqueous layer was separated and the remaining organic phase was diluted with heptane and washed sequentially with ice cold aqueous NaOH (320 g of 50% NaOH and 1 kg of ice), water, saturated NH4Cl and water. The solution was dried by azeotropic distillation and the product was purified by vacuum distillation to afford 395.7 g (93.7%) lib contaminated with 3-6% 3-(tert-butyl-dimethylsilyloxy)-bromobenzene.

Reference： [1]Current Patent Assignee: ROCHE HOLDING AG - US2009/12034, 2009, A1 Location in patent: Page/Page column 16
[2]Current Patent Assignee: ROCHE HOLDING AG - WO2008/145562, 2008, A1 Location in patent: Page/Page column 36-37

31
[ 97-94-9 ]
[ 65423-56-5 ]
[ 1204242-96-5 ]

Yield	Reaction Conditions	Operation in experiment
91%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; caesium carbonate In N,N-dimethyl-formamide at 60℃; for 3h; Inert atmosphere;

Reference： [1]Location in patent: experimental part Wang, Bing; Sun, Hui-Xia; Sun, Zhi-Hua; Lin, Guo-Qiang [Advanced Synthesis and Catalysis, 2009, vol. 351, # 3, p. 415 - 422]

32
[ 86-90-8 ]
[ 65423-56-5 ]
[ 868694-00-2 ]
[ 868693-98-5 ]

Yield	Reaction Conditions	Operation in experiment
		4-Bromo-2-(3 tbutyldimethylsilyloxy-benzoyl)-benzoic acid and 5-Bromo-2-(3- tbutyldimethylsilyloxy-benzoyl)-benzoic acid; A solution of TBS-protected 3-bromophenol (156.6 g, 0.54 mol) in anhydrous THF (160 ml) was added dropwise to a stirring suspension of magnesium turnings (13 g, 0.54 mol) in dry THF (240 ml). The Grignard formation initiated following the addition of 1 ml of solution. The resulting mixture was left stirring until the reflux had stopped, and then this was added in a single portion to a stirred solution of <strong>[86-90-8]4-bromophthalic anhydride</strong> (122.4 g, 0.54 mol) in anhydrous THF (240 ml). The reaction mixture was heated at reflux temperature overnight. After cooling to RT, the reaction was quenched by the addition of sat. aq. solution of ammonium chloride (250 ml) and the organics were extracted into ethyl acetate (3 x 250 ml). The combined organic extracts were dried (MgS04), filtered and concentrated in vacuo to provide the crude acid as a brown oil (226.6 g). The crude material was carried through to the next step without further purification. No.H (CDCl3; 250MHz) 8.07-6.75 (7H, m, aromatics), 0.99-0.94 (9H, m, C(CH3)3), 0.20-0.13 (6H, m, 2 x CH3).

Reference： [1]Patent: WO2005/103019,2005,A1 .Location in patent: Page/Page column 21

33
[ 65423-56-5 ]
[ 120-92-3 ]
C₁₇H₂₈O₂Si [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With iodine; magnesium In diethyl ether Reflux; Stage #2: cyclopentanone In diethyl ether for 1h; Stage #3: With hydrogenchloride In diethyl ether; water	51.1 A mixture of the TBS ether (720rag, 2.5mmol), magnesium (120mg, 4.94mmol), and small amount of iodine in Et2θ was heated to reflux to generate Grignard reagent. To the mixture was added eye1opentanone (230mg, 2.7mmol). After Ih stirring, the mixture was poured into aq. HCl and extracted with EtOAc. The organic layer was dried over anhydrous MgSU4, filtered, and concentrated under reduced pressure.

Reference： [1]Current Patent Assignee: AMOREPACIFIC CORP. - WO2010/2209, 2010, A2 Location in patent: Page/Page column 88

34
[ 65423-56-5 ]
[ 411235-57-9 ]
[ 1202643-51-3 ]

Yield	Reaction Conditions	Operation in experiment
90%	With potassium phosphate; tricyclohexylphosphine;palladium diacetate; In water; toluene; at 110℃; for 3h;	A suspension of (3-bromo-phenoxy)-tert-butyl-dimethyl-silane (500 nig, 0.1.74 mmol), <strong>[411235-57-9]cyclopropyl boronic acid</strong> (194 mg, 2.26 mmol), K3Ptheta4(1.3 g, 6.1 mmol), PCy3(49mg, 0.17mmol) , and Pd(OAc)2 (20mg, 0.087 mmol) in toluene/water (8ml/0.4ml) was stirred 3 hours at HOV and then diluted with Et2O. The organic layer was washed with water and brine, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The crude residue was purified by column chromatography (gradient 12% to 100% EtOAc in n- hexane) to give tert-butyl-(3-cyclopropyl-phenoxy)-dimethyl-silane (390 mg, 90 %) .<61 I > 1H NMROOOMHz, CDCl3): 67.15 ~ 7.09 (m, IH), 6.71 (d, IH, J = 7.8 Hz),6.47 (dd, IH, J = 7.8, 1.5 Hz), 6.56 (s, IH), 1.91 ~ 1.84 (m, IH)1 1.01 (s, 9H), 0.98 ~ 0.94 (m, 2H), 0.72 ~ 0.68 (m, 2H), 0.22 (s, 6H).
41%	With potassium phosphate; palladium diacetate; tricyclohexylphosphine; In water; toluene; at 110℃;	A suspension of (3-bromophenoxy)(tert-butyl)dimethylsilane (5.46 g, 19 mmol), <strong>[411235-57-9]cyclopropylboronic acid</strong> (2.i2 g, 24.7 mmol), potassium phosphate, tribasic (14.1 g, 66.5 mmol), tricyclohexylphosphine (0.53 g, 1 .9 mmol) and Pd(OAc)2 (0.21 g, 0.95 mmol) in toluene (80 mL) and water (4 mL) was stirred at 110 C overnight. The slurry was diluted with diethyl ether and washed with water and brine. The organic phase was dried (Mg504), filtered and concentrated.The crude was purified by flash column chromatography (EtOAc/ hexane) which gave the title compound (1.94 g, 41%).
41%	With potassium phosphate; palladium diacetate; tricyclohexylphosphine; In water; toluene; at 110℃;	A suspension of (3-bromophenoxy)(tert-butyl)dimethylsilane (5.46 g, 19 mmol),<strong>[411235-57-9]cyclopropylboronic acid</strong> (2.12 g, 24.7 mmol), potassium phosphate, tribasic (14.1 g, 66.5 mmcl), tricyclohexylphosphine (0.53 g, 1.9 mmcl) and Pd(OAc)2 (0.21 g, 0.95 mmcl) in toluene (80 mL) and water (4 mL) was stirred at 110 C overnight. The slurry was diluted with diethyl ether and washed with water and brine. The organic phase was dried (MgSO4), filtered and concentrated. The crude was purified by flash column chromatography (EtOAc hexane) which gave the titlecompound (1.94 g, 41%).

41%	With potassium phosphate; palladium diacetate; tricyclohexylphosphine; In water; toluene; at 110℃;	A suspension of (3-bromophenoxy)(tert-butyl)dimethylsilane (5.46 g, 19 mmol), <strong>[411235-57-9]cyclopropylboronic acid</strong> (2.12 g, 24.7 mmol), potassium phosphate, tribasic (14.1 g, 66.5 mmol), tricyclohexylphosphine (0.53 g, 1 .9 mmol) and Pd(OAc)2 (0.21 g, 0.95 mmol) in toluene (80 mL) and water (4 mL) was stirred at 1 10 C overnight. The slurry was diluted with diethyl ether and washed with water and brine. The organic phase was dried (MgS04), filtered and concentrated. The crude was purified by flash column chromatography (EtOAc/ hexane) which gave the title compound (1 .94 g, 41 %).
41%	With potassium phosphate; palladium diacetate; tricyclohexylphosphine; In water; toluene; at 110℃;	(3-Bromophenoxy)(tertbutyl)dimethylsilane (5.46 g, 19 mmol),Cyclopropylheptanoic acid (2.12 g, 24.7 mmol), tripotassium phosphate (14.1 g, 66.5 mmol), tricyclohexylphosphine (0.53 g, 1.9 mmol) and Pd (OAc) 2 (0.21 g, 0.95 mmol) in The suspension in toluene (80 mL) and water (4 mL) was stirred at 110 C overnight. The slurry was diluted with diethyl ether and washed with water and brine. The organic phase was dried (MgSO4), filtered and concentrated. The crude was purified by flash column chromatography (EtOAc / hexane), which gave the title compound (1.94 g, 41%).

Reference： [1]Patent: WO2010/2209,2010,A2 .Location in patent: Page/Page column 67
[2]Patent: WO2015/34420,2015,A1 .Location in patent: Page/Page column 52
[3]Patent: WO2015/56213,2015,A1 .Location in patent: Page/Page column 54
[4]Patent: WO2016/30335,2016,A1 .Location in patent: Page/Page column 35
[5]Patent: TW2018/15396,2018,A .Location in patent: Page/Page column 62

35
[ 6026-02-4 ]
[ 65423-56-5 ]
C₁₈H₃₅NOSi₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With tert.-butyl lithium In tetrahydrofuran; pentane at -78℃; Inert atmosphere; Stage #2: (N,N-diethylamino)dimethylchlorosilane In tetrahydrofuran; pentane at -78℃; for 2h; Inert atmosphere;

Reference： [1]Bracegirdle, Sonia; Anderson, Edward A. [Chemical Communications, 2010, vol. 46, # 20, p. 3454 - 3456]

36
[ 1254223-99-8 ]
[ 65423-56-5 ]
[ 1254224-06-0 ]

Yield	Reaction Conditions	Operation in experiment
58%	Stage #1: C₁₆H₂₅N₃O₄S With water; palladium diacetate; lithium tert-butoxide; XPhos In 1,4-dioxane for 0.0166667h; Inert atmosphere; Stage #2: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene In 1,4-dioxane at 110℃; for 4h; Inert atmosphere; optical yield given as %ee; regioselective reaction;

Reference： [1]Barluenga, Jose; Escribano, Maria; Aznar, Fernando; Valde, Carlos [Angewandte Chemie - International Edition, 2010, vol. 49, # 38, p. 6856 - 6859]

37
[ 65423-56-5 ]
[ 677-22-5 ]
[ 18052-27-2 ]
[ 1254941-68-8 ]

Yield	Reaction Conditions	Operation in experiment
1: 67% 2: 29 mg	With 1.54H₂O*Cl₂Ni; 1,3-bis(cyclohexyl)imidazolium tetrafluoroborate In tetrahydrofuran at -10℃; for 1.5h; Inert atmosphere;

Reference： [1]Joshi-Pangu, Amruta; Wang, Chao-Yuan; Biscoe, Mark R. [Journal of the American Chemical Society, 2011, vol. 133, # 22, p. 8478 - 8481]

38
[ 65423-56-5 ]
[ 933-88-0 ]
[ 1447932-31-1 ]

Yield	Reaction Conditions	Operation in experiment
75%	Stage #1: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With diisobutylaluminum chloride In tetrahydrofuran at -78℃; Inert atmosphere; Schlenk technique; Stage #2: With n-butyllithium In tetrahydrofuran; hexane at -78 - 20℃; Inert atmosphere; Schlenk technique; Stage #3: ortho-toluoyl chloride With copper(I) cyanide di(lithium chloride) In tetrahydrofuran; hexane at -40 - 25℃; Inert atmosphere;

Reference： [1]Klatt, Thomas; Groll, Klaus; Knochel, Paul [Chemical Communications, 2013, vol. 49, # 62, p. 6953 - 6955]

39
[ 65423-56-5 ]
[ 7646-85-7 ]
(3-((tert-butyldimethylsilyl)oxy)phenyl)zinc chloride [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
88%	Stage #1: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With magnesium; lithium chloride In tetrahydrofuran at 25℃; Inert atmosphere; Schlenk technique; Stage #2: zinc(II) chloride In tetrahydrofuran at 0 - 25℃; for 0.25h; Inert atmosphere; Schlenk technique;
	Stage #1: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With n-butyllithium In tetrahydrofuran at -78℃; for 0.166667h; Inert atmosphere; Stage #2: zinc(II) chloride In tetrahydrofuran at 20℃; for 0.666667h; Inert atmosphere;
	With magnesium; lithium chloride In tetrahydrofuran at 0℃; Inert atmosphere;

Stage #1: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With magnesium; lithium chloride In tetrahydrofuran at 0℃; for 2h; Schlenk technique; Inert atmosphere; Stage #2: zinc(II) chloride In tetrahydrofuran at 0 - 20℃; for 0.25h; Schlenk technique; Inert atmosphere;

Reference： [1]Graßl, Simon; Knochel, Paul [Organic Letters, 2020]
[2]Liang, Yufan; Fu, Gregory C. [Journal of the American Chemical Society, 2014, vol. 136, # 14, p. 5520 - 5524]
[3]Haas, Diana; Hammann, Jeffrey M.; Lutter, Ferdinand H.; Knochel, Paul [Angewandte Chemie - International Edition, 2016, vol. 55, # 11, p. 3809 - 3812][Angew. Chem., 2016, vol. 128, p. 3873 - 3877,5]
[4]Hofmayer, Maximilian S.; Sunagatullina, Alisa; Brösamlen, Daniel; Mauker, Philipp; Knochel, Paul [Organic Letters, 2020, vol. 22, # 4, p. 1286 - 1289]

40
[ 65423-56-5 ]
3-(t-butyldimethylsilanyloxy)phenyllithium [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With tert.-butyl lithium In diethyl ether; pentane at -80℃; for 1.5h; Schlenk technique; Inert atmosphere;

Reference： [1]Sosnicki, Jacek G.; Struk, Lukasz; Kurzawski, Mateusz; Peruzynska, Magdalena; Maciejewska, Gabriela; Drozdzik, Marek [Organic and Biomolecular Chemistry, 2014, vol. 12, # 21, p. 3427 - 3440]

41
[ 65423-56-5 ]
[ 58287-77-7 ]
[ 155765-75-6 ]

Yield	Reaction Conditions	Operation in experiment
54%	Stage #1: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Stage #2: N,N-diethyl-4-formylbenzamide In tetrahydrofuran; hexane at 20℃; for 3h;	1 10305] N,N-Diethyl-4-[hydroxy-(3-O-TI3DMS-phenyl)-methyl]benzamide (3) 10305] N,N-Diethyl-4-[hydroxy-(3-O-TI3DMS-phenyl)-methyl]benzamide (3): Compound 2 (1.55 g, 5.42 mmol) was dissolved in anhydrous THF (30 ml). At -78° C., n-l3uLi solution (3.44 ml, 5.5 mmol, 1.6 M in Hexanes solution) was added dropwise. Afier 30 minutes, a solution of compound 1 (1.13 g, 5.50 mmol) in THF (8 ml) was added dropwise with stirring. The reaction solution was allowed to warm up toroom temperature in a period of 3 hrs. Then a saturated NH4C1 solution (5 ml) was added to quench the reaction. The solution was extracted with DCM (20 mlx3). The organic phases were combined, dried over Na2SO4, filtered, and the solvent removed under reduced pressure. The resulting residue was subjected to flash chromatography (EtOAc/Hexanes=12%.- 60%) to give compound 3 (1.23 g, 2.97 mmol, yield 54%). ‘H NMR (CDC13): ö 7.33 (d, 2H), 7.23 (d, 2H), 7.15-7.12 (m, 1H), 6.94-6.91 (m, 1H), 6.84-6.83 (m, 1H),6.73-6.70 (m, 1H), 5.69 (d, 1H), 3.73 (d, 1H), 3.48 (m, 2H),3.22 (m, 2H), 1.19 (m, 3H), 1.08 (m, 3H), 0.97 (s, 9H), 0.15 (s, 6H).

Reference： [1]Current Patent Assignee: NEKTAR THERAPEUTICS - US2015/335640, 2015, A1 Location in patent: Paragraph 0305

42
[ 65423-56-5 ]
[ 89-98-5 ]
C₁₉H₂₅ClO₂Si [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With iodine; magnesium Stage #2: 2-chloro-benzaldehyde In tetrahydrofuran at -40 - 20℃; Schlenk technique; Inert atmosphere;

Reference： [1]Chen, Jianhui; Chen, Chenhui; Ji, Chonglei; Lu, Zhan [Organic Letters, 2016, vol. 18, # 7, p. 1594 - 1597]

43
[ 65423-56-5 ]
C₂₀H₂₃NO₂ [ No CAS ]
C₃₂H₄₃NO₃Si [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: C₂₀H₂₃NO₂ In tetrahydrofuran; hexane at -78℃; for 2h; Inert atmosphere;

Reference： [1]Shen, Qing; Qian, Yuanyuan; Huang, Xiaoqin; Xu, Xuejun; Li, Wei; Liu, Jinggen; Fu, Wei [ACS Medicinal Chemistry Letters, 2016, vol. 7, # 4, p. 391 - 396]

44
(RS)-2-dimethylaminomethyl-6-(3-methoxy-phenyl)-3,4-dihydro-2H-naphthalen-1-one [ No CAS ]
[ 65423-56-5 ]
C₃₂H₄₃NO₃Si [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: (RS)-2-dimethylaminomethyl-6-(3-methoxy-phenyl)-3,4-dihydro-2H-naphthalen-1-one In tetrahydrofuran; hexane at -78℃; for 2h; Inert atmosphere;

Reference： [1]Shen, Qing; Qian, Yuanyuan; Huang, Xiaoqin; Xu, Xuejun; Li, Wei; Liu, Jinggen; Fu, Wei [ACS Medicinal Chemistry Letters, 2016, vol. 7, # 4, p. 391 - 396]

45
[ 65423-56-5 ]
C₂₀H₂₃NO₂ [ No CAS ]
C₃₂H₄₃NO₃Si [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: C₂₀H₂₃NO₂ In tetrahydrofuran; hexane at -78℃; for 2h; Inert atmosphere;

Reference： [1]Shen, Qing; Qian, Yuanyuan; Huang, Xiaoqin; Xu, Xuejun; Li, Wei; Liu, Jinggen; Fu, Wei [ACS Medicinal Chemistry Letters, 2016, vol. 7, # 4, p. 391 - 396]

46
[ 65423-56-5 ]
C₂₀H₂₀F₃NO [ No CAS ]
C₃₂H₄₀F₃NO₂Si [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: C₂₀H₂₀F₃NO In tetrahydrofuran; hexane at -78℃; for 2h; Inert atmosphere;

Reference： [1]Shen, Qing; Qian, Yuanyuan; Huang, Xiaoqin; Xu, Xuejun; Li, Wei; Liu, Jinggen; Fu, Wei [ACS Medicinal Chemistry Letters, 2016, vol. 7, # 4, p. 391 - 396]

47
[ 65423-56-5 ]
C₁₉H₂₀ClNO [ No CAS ]
C₃₁H₄₀ClNO₂Si [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: C₁₉H₂₀ClNO In tetrahydrofuran; hexane at -78℃; for 2h; Inert atmosphere;

Reference： [1]Shen, Qing; Qian, Yuanyuan; Huang, Xiaoqin; Xu, Xuejun; Li, Wei; Liu, Jinggen; Fu, Wei [ACS Medicinal Chemistry Letters, 2016, vol. 7, # 4, p. 391 - 396]

48
[ 65423-56-5 ]
C₁₉H₁₉Cl₂NO [ No CAS ]
C₃₁H₃₉Cl₂NO₂Si [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: C₁₉H₁₉Cl₂NO In tetrahydrofuran; hexane at -78℃; for 2h; Inert atmosphere;

Reference： [1]Shen, Qing; Qian, Yuanyuan; Huang, Xiaoqin; Xu, Xuejun; Li, Wei; Liu, Jinggen; Fu, Wei [ACS Medicinal Chemistry Letters, 2016, vol. 7, # 4, p. 391 - 396]

49
[ 65423-56-5 ]
C₂₀H₂₃NO [ No CAS ]
C₃₂H₄₃NO₂Si [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: C₂₀H₂₃NO In tetrahydrofuran; hexane at -78℃; for 2h; Inert atmosphere;

Reference： [1]Shen, Qing; Qian, Yuanyuan; Huang, Xiaoqin; Xu, Xuejun; Li, Wei; Liu, Jinggen; Fu, Wei [ACS Medicinal Chemistry Letters, 2016, vol. 7, # 4, p. 391 - 396]

50
[ 65423-56-5 ]
C₁₉H₂₀FNO [ No CAS ]
C₃₁H₄₀FNO₂Si [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: C₁₉H₂₀FNO In tetrahydrofuran; hexane at -78℃; for 2h; Inert atmosphere;

Reference： [1]Shen, Qing; Qian, Yuanyuan; Huang, Xiaoqin; Xu, Xuejun; Li, Wei; Liu, Jinggen; Fu, Wei [ACS Medicinal Chemistry Letters, 2016, vol. 7, # 4, p. 391 - 396]

51
[ 65423-56-5 ]
C₁₉H₂₀ClNO [ No CAS ]
C₃₁H₄₀ClNO₂Si [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: C₁₉H₂₀ClNO In tetrahydrofuran; hexane at -78℃; for 2h; Inert atmosphere;

Reference： [1]Shen, Qing; Qian, Yuanyuan; Huang, Xiaoqin; Xu, Xuejun; Li, Wei; Liu, Jinggen; Fu, Wei [ACS Medicinal Chemistry Letters, 2016, vol. 7, # 4, p. 391 - 396]

52
[ 65423-56-5 ]
6-allyl-5-iodo-2,4-dimethoxy-7-tosyl-7H-pyrrolo[2,3-d]pyrimidine [ No CAS ]
6-allyl-5-(3-((tert-butyldimethylsilyl)oxy)phenyl)-2,4-dimethoxy-7-tosyl-7H-pyrrolo[2,3-d]pyrimidine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
52%	Stage #1: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With TurboGrignard In tetrahydrofuran at 0℃; for 1h; Inert atmosphere; Stage #2: With zinc(II) chloride In tetrahydrofuran at 25℃; for 0.25h; Inert atmosphere; Stage #3: 6-allyl-5-iodo-2,4-dimethoxy-7-tosyl-7H-pyrrolo[2,3-d]pyrimidine With [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(ll) dichloride In tetrahydrofuran at 50℃; for 24h; Inert atmosphere;

Reference： [1]Nickel, Johannes; Fernández, Maitane; Klier, Lydia; Knochel, Paul [Chemistry - A European Journal, 2016, vol. 22, # 40, p. 14397 - 14400]

53
[ 141831-51-8 ]
[ 65423-56-5 ]
(R)-quinuclidin-3-yl 2-(3-((tert-butyldimethylsilyl)oxy)phenyl)-2-hydroxy-2-phenylacetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78.5%	Stage #1: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With iodine; magnesium In tetrahydrofuran for 2h; Reflux; Stage #2: (3R)-1-azabicyclo[2.2.2]oct-3-yl oxo(phenyl)acetate In tetrahydrofuran at -75 - 20℃;	3 Step 3; (R)-Quinuclidin-3-yl 2-(3-((tert-butyldimethylsilyl)oxy)phenyl)-2-hydroxy-2-phenylacetate Magnesium turnings (8.58 g, 0.36 mol, 1.5 eq) and iodine (catalytic) were suspended in anhydrous THF (460 mE) under argon and a solution of (3-bromophenoxy)(tert- butyl)dimethylsilane (88.01 g, 0.306 mol, 1.2 eq) in anhydrous THF (175 mE) added drop-wise. The reaction mixture was stirred at reflux for 2 hours. The reaction mixture was cooled to room temperature and then added drop-wise via a syringe pump to a solution of (R)-quinuclidin-3-yl 2-oxo-2- phenylacetate (66.2 g, 0.26 mol, 1 eq) in anhydrous THF (660 mE) at -75° C. over 2 hours. The reaction mixture was allowed to warm to room temperature and then stirred overnight. The reaction mixture was cooled to 0° C. and quenched with saturated aqueous ammonium chloride (500 mE). The reaction mixture was extracted with ethyl acetate and the organic phase was washed with brine, dried over anhydrous magnesium sulfate and the filtrate evaporated under reduced pressure. The residue was purified by flash column chromatography (eluent-1 00% DCM to 20:1 DCMlmethanol) to afford the title product (66.2 g, 78.5%).10424] ‘H NMR (400 MHz, DMSO-d5) ö 7.37-7.28 (m,5H), 7.25-7.20 (m, 1H), 7.01-6.95 (m, 1H), 6.83-6.76 (m,2H), 6.60 (s, 1H), 4.84-4.78 (m, 1H), 3.12-3.06 (m, 1H),2.65-2.56 (m, 3H), 2.48-2.37 (m, 2H), 1.90-1.80 (m, 1H),1.59-1.42 (m, 2H), 1.36-1.30 (m, 1H), 1.21-1.12 (m, 1H),0.92-0.89 (m, 9H), 0.12 (d, J=1.0 Hz, 6H).

Reference： [1]Current Patent Assignee: Valline SRL - US2016/235734, 2016, A1 Location in patent: Paragraph 0422; 0423; 0424

54
[ 65423-56-5 ]
2-iodo-4-methyl-1-(prop-1-en-2-yl)cyclohexane [ No CAS ]
tert-butyldimethyl(3-((1R,2R,5R)-5-methyl-2-(prop-1-en-2-yl)cyclohexyl)phenoxy)silane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
77%	Stage #1: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With magnesium; lithium chloride In tetrahydrofuran at 0℃; Stage #2: 2-iodo-4-methyl-1-(prop-1-en-2-yl)cyclohexane With 2.9-dimethyl-1,10-phenanthroline; Cl(x)Co(x)Li(x) In tetrahydrofuran at 0℃; for 8h; Inert atmosphere; Schlenk technique; diastereoselective reaction;

Reference： [1]Hammann, Jeffrey M.; Haas, Diana; Tüllmann, Carl-Phillip; Karaghiosoff, Konstantin; Knochel, Paul [Organic Letters, 2016, vol. 18, # 19, p. 4778 - 4781]

55
[ 65423-56-5 ]
[ 1395881-50-1 ]
C₂₇H₄₄O₂Si [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With tert.-butyl lithium In diethyl ether at -78 - 20℃;

Reference： [1]Kuan, Kevin K. W.; Hirschvogel, Aylin M.C.; George, Jonathan H. [Australian Journal of Chemistry, 2016, vol. 69, # 12, p. 1420 - 1423]

56
lithium manganese chloride [ No CAS ]
[ 65423-56-5 ]
di(3-(TBSO)benzene-1-yl)manganese [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With iodine; magnesium; lithium chloride In tetrahydrofuran at 0 - 20℃; for 1h; Inert atmosphere;

Reference： [1]Hofmayer, Maximilian S.; Hammann, Jeffrey M.; Haas, Diana; Knochel, Paul [Organic Letters, 2016, vol. 18, # 24, p. 6456 - 6459]

57
[ 65423-56-5 ]
[ 62952-33-4 ]
3'-((tert-butyldimethylsilyl)oxy)-4-ethoxy-1-methyl-5,6-dihydro-[1,1'-biphenyl]-2(1H)-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
95%	Stage #1: 3-ethoxy-6-methylcyclohex-2-en-1-one With lithium hexamethyldisilazane In toluene at -20℃; for 0.5h; Inert atmosphere; Stage #2: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With chloro[(tri-tert-butylphosphine)-2-(2-aminobiphenyl)]palladium (II) In toluene at -20 - 20℃; for 4.16667h; Inert atmosphere; Schlenk technique;

Reference： [1]Johnson, Thomas; Pultar, Felix; Menke, Friedericke; Lautens, Mark [Organic Letters, 2016, vol. 18, # 24, p. 6488 - 6491]

58
[ 65423-56-5 ]
[ 207681-67-2 ]
[ 1258203-31-4 ]

Yield	Reaction Conditions	Operation in experiment
91%	Stage #1: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With n-butyllithium In tetrahydrofuran at -78℃; for 1.33333h; Stage #2: N-methoxy-N-methyl-3-bromobenzamide In tetrahydrofuran at -78℃; for 2h;	1 Synthesis of 13 -(t-Butyldimethylsilyl)oxyphenyll-(3 -bromophenyl) methanone The (3-bromophenoxy)-tert-butyl-dimethyl-silane (3.905 g, 13.59 mmol) was dissolved in THF (20 mL) and stirred for 5 mm. The solution was cooled to -78 °C and stirred for an additional 10 mmbefore dropwise addition of n-butyllithium (2.96 mL, 6.8 mmol). The solution was allowed to stir for 1 hour and 20 minutes. A solution of 3-Bromo-N-methoxy-N-methylbenzamide (1.508 g, 6.17 mmol) in 5 mL THF was added and allowed to stir for 2 hours at -78 °C. It is noted that the organo-lithium reagent can be added to the benzamide reagent in a reverse addition protocol. The ice bath was removed and the reaction mixture was allowed to stir for 30 minutes. The reaction mixture was quenched with 20 mL of 1M HCI, and the organic phase was extracted with chloroform (2 x 50 mL). The organic phase was washed three times with saturated sodium bicarbonate. The organic phase was separated, dried over sodium sulfate, and concentrated under reduced pressure. Purification by flash column chromatography (silica gel, hexanes :EtOAc, gradient 100:0 to 85:15) afforded [3-(t-Butyldimethylsilyl)oxyphenyl]-(3 - bromophenyl)methanone (2.184 g, 5.58 mmol, 91% yield). 1H NMR (600 MHz, DMSO-d6) 67.89 (1H,ddd,J= 8.0 Hz, 2.1 Hz, 1.0 Hz), 7.83 (IH, t, J 1.8 Hz), 7.71 (IH, ddd, J= 7.7 Hz, 1.6 Hz, 1.0 Hz), 7.53(1H, t, J 7.9 Hz), 7.47 (IH, t, J 7.9 Hz), 7.34 (lH, ddd, J= 7.6 Hz, 1.6 Hz, 1.0 Hz), 7.20 (IH, ddd, J8.1 Hz, 2.6 Hz, 1.0 Hz), 7.14 (IH, dd, J= 2.5 Hz, 1.6 Hz), 0.95 (s, 9H), 0.20 (s, 6H). 13C NMR (150MHz, DMSO-d6) 8 193.90, 155.11, 139.16, 137.84, 135.32, 131.84, 130.82, 130.19, 128.56, 124.80,123.09, 121.80, 120.57, 25.55, 18.01, -4.54.
91%	Stage #1: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With n-butyllithium In tetrahydrofuran at -78℃; for 1.33333h; Inert atmosphere; Stage #2: N-methoxy-N-methyl-3-bromobenzamide In tetrahydrofuran at -78℃; for 2.5h; Inert atmosphere;	[3-(t-Butyldimethylsilyl)oxyphenyl]-(3-bromophenyl)methanone (9).6 The (3-bromophenoxy)-tert-butyl-dimethyl-silane (3.905 g, 13.59 mmol) was dissolved in THF (20 mL) and stirred for 5 min. The solution was cooled to -78° C and stirred for anadditional 10 min before dropwise addition of n-butyllithium (2.96 mL, 6.8 mmol). The solution was allowed to stir for 1 h and 20 m. A solution of 3-Bromo-N-methoxy-N-methylbenzamide(1.508 g, 6.17 mmol) in 5 mL THF was added and allowed to stir for 2 h at -78° C . The ice bath was removed and the reaction mixture was allowed to stir for 30 minutes. The reaction mixture was quenched with 20 mL of 1 M HCl, and the organic phase was extracted with chloroform (2 x50 mL). The organic phase was washed three times with saturated sodium bicarbonate. Theorganic phase was separated, dried over sodium sulfate, and concentrated under reduced pressure. Purification by flash column chromatography (silica gel, hexanes:EtOAc, gradient100:0 to 85:15) afforded [3-(t-Butyldimethylsilyl)oxyphenyl]-(3-bromophenyl)methanone (2.184g, 5.58 mmol, 91% yield).

Reference： [1]Current Patent Assignee: BAYLOR UNIVERSITY - WO2017/30983, 2017, A1 Location in patent: Paragraph 0153; 0158; 0159
[2]Parker, Erica N.; Odutola, Samuel O.; Wang, Yifan; Strecker, Tracy E.; Mukherjee, Rajeswari; Shi, Zhe; Chaplin, David J.; Trawick, Mary Lynn; Pinney, Kevin G. [Bioorganic and Medicinal Chemistry Letters, 2017, vol. 27, # 5, p. 1304 - 1310]

59
[ 65423-56-5 ]
[ 1400755-05-6 ]
(3'-((tert-butyldimethylsilyl)oxy)-2-methyl-[1,1'-biphenyl]-3-yl)methanol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
97%	With potassium phosphate; XPhos In tetrahydrofuran; water at 20℃; for 16h; Inert atmosphere;	Intermediate: (3'-((tert-butyldimethylsilyl)oxy)-2-methyl-[1,1'-biphenyl]-3-yl)methanol Intermediate: (3'-((tert-butyldimethylsilyl)oxy)-2-methyl-[1,1'-biphenyl]-3-yl)methanol A mixture of (3-bromophenoxy)(tert-butyl)dimethylsilane (1.2 g, 4.18 mmol) and (2-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)methanol (1.036 g, 4.18 mmol) in THF (25 ml) and 0.5 M aq potassium phosphate, tribasic (25.06 ml, 12.53 mmol) was stirred under N2 sparging for 15 min, then added with 2nd gen. XPhos precatalyst (0.099 g, 0.125 mmol), sparging was continued for 10 min. The reaction mixture was stirred at rt under N2 for 16 h. The reaction was diluted with EtOAc, washed with brine, dried over anhydrous Na2SO4, filtered and concentrated to yield a dark oil, which was purified on silica gel (0-70% EtOAc/hex) to yield (3'-((tert-butyldimethylsilyl)oxy)-2-methyl-[1,1'-biphenyl]-3-yl)methanol (1.33 g, 97% yield). LC/MS (Cond. N-1): [M-OH]+311.3, RT=4.74 min.

Reference： [1]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - US2017/107202, 2017, A1 Location in patent: Paragraph 0354; 0355

60
[ 112-29-8 ]
[ 2050-77-3 ]
[ 65423-56-5 ]
C₂₂H₄₀OSi [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	Stage #1: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With n-butyllithium In tetrahydrofuran at -78℃; for 1h; Inert atmosphere; Stage #2: 1-bromo dodecane; Iododecane In tetrahydrofuran at 20℃; Inert atmosphere;

Reference： [1]He, Zhen; Shrives, Harry J.; Fernández-Salas, José A.; Abengózar, Alberto; Neufeld, Jessica; Yang, Kevin; Pulis, Alexander P.; Procter, David J. [Angewandte Chemie - International Edition, 2018, vol. 57, # 20, p. 5759 - 5764][Angew. Chem., 2018, vol. 57, # 130, p. 5861 - 5866,6]

61
[ 37490-22-5 ]
[ 65423-56-5 ]
C₁₈H₃₀OSi [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
96%	With [(bis(3,5-di-tert-butylphenyl)(tert-butyl)phosphine)₂PdCl₂]; caesium carbonate In tetrahydrofuran; water at 70℃; for 2h; Schlenk technique; Inert atmosphere;

Reference： [1]Reid, William B.; Watson, Donald A. [Organic Letters, 2018, vol. 20, # 21, p. 6832 - 6835]

62
[ 610-96-8 ]
[ 65423-56-5 ]
C₃₁H₄₃ClO₃Si₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 1-bromo-3-[(tert-butyldimethylsilyl)oxy]benzene With magnesium; ethylene dibromide In tetrahydrofuran for 2h; Inert atmosphere; Reflux; Stage #2: methyl chlorobenzoate In tetrahydrofuran at 5℃; for 0.833333h; Inert atmosphere; Reflux;	2.2-a Example (2-a) TBS2-2-ClTrt-OH 4.48 g (15.6 mmol) of 1-bromo-3-[[(1,1-dimethylethyl)dimethylsilyl]oxy]benzene was dissolved in 31.2 mL of anhydrous THF, and 455 mg (18.7 mmol) of magnesium was added thereto. The interior of the reaction container was purged with nitrogen, subsequently 7 μL (0.08 mmol) of 1,2-dibromoethane was added thereto, and the mixture was heated to reflux for 2 hours. The reaction solution was cooled to 50° C., 1.00 g (5.9 mmol) of methyl 2-chlorobenzoate dissolved in 7.8 mL of anhydrous THF was added thereto, and the mixture was heated to reflux for 50 minutes. The reaction solution was cooled to 5° C., the reaction was stopped with 79 mL of a saturated aqueous solution of ammonium chloride, 224 mL of heptane was added thereto, and the mixture was partitioned and washed. An organic layer thus obtained was partitioned and washed once with 79 mL of a saturated aqueous solution of ammonium chloride and once with 116 mL of a 5% aqueous solution of sodium hydrogen carbonate. The organic layer was concentrated under reduced pressure, and thereby a mixture including TBS2-2-ClTrt-OH was obtained.

Reference： [1]Current Patent Assignee: SEKISUI CHEMICAL CO., LTD. - US2019/308997, 2019, A1 Location in patent: Paragraph 0085; 0087

63
[ 65423-56-5 ]
[ 225916-39-2 ]
C₁₈H₂₃FOSi [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
93%	With P(t-Bu)3 Palladacycle Gen_. 3; potassium trimethylsilonate In tetrahydrofuran at 23℃; for 0.0833333h;

Reference： [1]Delaney, Connor P.; Kassel, Vincent M.; Denmark, Scott E. [ACS Catalysis, 2020, vol. 10, # 1, p. 73 - 80]

64
[ 65423-56-5 ]
bis(2-bromo-5-((tert-butyldimethylsilyl)oxy)phenyl)dimethylsilane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1.1: n-butyllithium / tetrahydrofuran; hexane / 1.42 h / -78 °C 1.2: 2 h / 20 °C 2.1: pyridine; N-Bromosuccinimide / acetonitrile / 24 h / 60 °C
	Multi-step reaction with 2 steps 1.1: n-butyllithium / tetrahydrofuran; hexane / 0.5 h / -78 °C / Inert atmosphere 1.2: -78 - 20 °C / Inert atmosphere 2.1: N-Bromosuccinimide / N,N-dimethyl-formamide / 20 °C

Reference： [1]Current Patent Assignee: UNIVERSITY OF ILLINOIS (SYSTEM) - US2020/199092, 2020, A1
[2]Chan, Jefferson; Ibarra, Gabriela E.; Krishnamurthy, Vishnu; Pino, Nicholas W.; Smaga, Lukas P. [Journal of the American Chemical Society, 2020]

65
[ 65423-56-5 ]
[ 1301205-25-3 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1.1: n-butyllithium / tetrahydrofuran; hexane / 1.42 h / -78 °C 1.2: 2 h / 20 °C 2.1: pyridine; N-Bromosuccinimide / acetonitrile / 24 h / 60 °C 3.1: tert.-butyl lithium / tetrahydrofuran; pentane / 0.67 h / -78 °C
	Multi-step reaction with 3 steps 1.1: n-butyllithium / tetrahydrofuran; hexane / 0.5 h / -78 °C / Inert atmosphere 1.2: -78 - 20 °C / Inert atmosphere 2.1: N-Bromosuccinimide / N,N-dimethyl-formamide / 20 °C 3.1: sec.-butyllithium / tetrahydrofuran; cyclohexane / 0.5 h / -78 °C / Inert atmosphere 3.2: -78 - 20 °C / Inert atmosphere

Reference： [1]Current Patent Assignee: UNIVERSITY OF ILLINOIS (SYSTEM) - US2020/199092, 2020, A1
[2]Chan, Jefferson; Ibarra, Gabriela E.; Krishnamurthy, Vishnu; Pino, Nicholas W.; Smaga, Lukas P. [Journal of the American Chemical Society, 2020]

66
[ 65423-56-5 ]
[ 1301205-24-2 ]