Name: 30506-30-0|1-Bromo-4-(Ethylthio)benzene|98%
Brand: Ambeed
SKU: A228808
Rating: 90 (35 reviews)

1
[ 917-95-3 ]
[ 30506-30-0 ]
[ 53104-02-2 ]

Reference： [1]Tetrahedron,1973,vol. 29,p. 3833 - 3843

2
[ 30506-30-0 ]
[ 118-92-3 ]
[ 74-85-1 ]
[ 65662-88-6 ]

Reference： [1]Chemistry Letters,1983,p. 249 - 250

3
[ 74-96-4 ]
[ 106-53-6 ]
[ 30506-30-0 ]

Yield	Reaction Conditions	Operation in experiment
96%	With triethylamine; In acetonitrile; for 17h;Reflux;	[00144] A mixture of 4-bromobenzenethiol (50 g, 0.26 mol), bromoethane (58 g, 0.53 mol) and triethylamine (78 g, 0.78 mol) in acetonitrile (1 L) was stirred at reflux for 17 h. The mixture was cooled to rt and filtered. The filtrate was concentrated under vacuum. The residue was purified by silica gel chromatography (eluting with petroleum ether) to give (4- bromophenyl)(ethyl)sulfane (55 g, 96%) as an oil. 1H NMR (CDC13, 400 MHz): δ 7.40-7.42 (dd, J = 6.4, 2.0 Hz, 2H), 7.18-7.20 (dd, J = 6.4, 2.0 Hz, 2H), 2.91-2.96 (q, J = 1.2 Hz, 2H), 1.30-1.33 (t, J = 7.2 Hz, 3H).
96%	With triethylamine; In acetonitrile; for 17h;Reflux;	A mixture of 4-bromobenzenethiol (50 g, 0.26 mol), bromoethane (58 g, 0.53 mol) and triethylamine (78 g, 0.78 mol) in acetonitrile (1 L) was stirred at reflux for 17 h. The mixture was cooled to rt and filtered. The filtrate was concentrated under vacuum. The residue was purified by silica gel chromatography (eluting with petroleum ether) to give (4-bromophenyl)(ethyl)sulfane (55 g, 96%) as an oil. 1H NMR (CDCl3, 400 MHz): δ 7.40-7.42 (dd, J=6.4, 2.0 Hz, 2H), 7.18-7.20 (dd, J=6.4, 2.0 Hz, 2H), 2.91-2.96 (q, J=7.2 Hz, 2H), 1.30-1.33 (t, J=7.2 Hz, 3H).
96%	With triethylamine; In acetonitrile; for 17h;Reflux;	A mixture of 4-bromobenzenethiol (50 g, 0.26 mol), bromoethane (58 g, 0.53 mol) and triethylamine (78 g, 0.78 mol) in acetonitrile (1 E) was stirred at reflux for 17 h. The mixture was cooled to it and filtered. The filtrate was concentrated under vacuum. The residue was purified by silica gel chromatography (eluting with petroleum ether) to give (4-bromophenyl)(ethyl)sulfane (55 g, 96%) as an oil. ‘H NMR (CDC13, 400 MHz): ö 7.40-7.42 (dd, J=6.4, 2.0 Hz,2H), 7.18-7.20 (dd, J=6.4, 2.0 Hz, 2H), 2.91-2.96 (q, J=7.2 Hz, 2H), 1.30-1.33 (t, J=7.2 Hz, 3H).

96%	With triethylamine; In acetonitrile; for 17h;Reflux;	A mixture of 4-bromobenzenethiol (50 g, 0.26 mol), bromoethane (58 g, 0.53 mol) and triethylamine (78 g, 0.78 mol) in acetonitrile (1 L) was stirred at reflux for 17 h. The mixture was cooled to rt and filtered. The filtrate was concentrated under vacuum. The residue was purified by silica gel chromatography (eluting with petroleum ether) to give (4- bromophenyl)(ethyl)sulfane (55 g, 96%) as an oil. 1H NMR (CDC13, 400 IVIHz): 5 7.40-7.42 (dd, J 6.4, 2.0 Hz, 2H), 7.18-7.20 (dd, J 6.4, 2.0 Hz, 2H), 2.91-2.96 (q, J= 7.2 Hz, 2H), 1.30-1.33 (t, J 7.2 Hz, 3H).
96%	With triethylamine; In acetonitrile; for 17h;Reflux;	[00199] Step 1: (4-bromophenyl)(ethyl)sulfane [0987] [00200] A mixture of 4-bromobenzenethiol (50 g, 0.26 mol), bromoethane (58 g, 0.53 mol) and triethylamine (78 g, 0.78 mol) in acetonitrile (1 L) was stirred at reflux for 17 h. The mixture was cooled to rt and filtered. The filtrate was concentrated under vacuum. The residue was purified by silica gel chromatography (eluting with petroleum ether) to give (4- bromophenyl)(ethyl)sulfane (55 g, 96%) as an oil. 1H NMR (CDC13, 400 MHz): δ 7.40-7.42 (dd, J = 6.4, 2.0 Hz, 2H), 7.18-7.20 (dd, J = 6.4, 2.0 Hz, 2H), 2.91-2.96 (q, J = 7.2 Hz, 2H), 1.30- 1.33 (t, 7 = 7.2 Hz, 3H).

Reference： [1]Patent: WO2016/61160,2016,A1 .Location in patent: Paragraph 00144
[2]Patent: US2016/122345,2016,A1 .Location in patent: Paragraph 0115; 0116
[3]Patent: US9481674,2016,B1 .Location in patent: Page/Page column 45; 46
[4]Patent: WO2017/87608,2017,A1 .Location in patent: Paragraph 00125; 00126
[5]Patent: WO2017/132432,2017,A1 .Location in patent: Paragraph 00199-00200
[6]European Journal of Organic Chemistry,2013,p. 5917 - 5922
[7]Chemistry Letters,1983,p. 249 - 250

4
[ 161573-75-7 ]
[ 30506-30-0 ]
4-bromophenyl prop-1-enyl sulfide [ No CAS ]

Reference： [1]Journal of the Chemical Society. Chemical communications,1994,p. 805 - 806

5
[ 97-93-8 ]
[ 98-58-8 ]
[ 30506-30-0 ]

Reference： [1]Organometallics in Chemical Synthesis,1970,vol. 1,p. 31 - 35

6
[ 161573-70-2 ]
[ 104-95-0 ]
[ 30506-30-0 ]

Reference： [1]Journal of the Chemical Society. Perkin transactions I,1999,p. 593 - 604
[2]Journal of the Chemical Society. Perkin transactions I,1999,p. 593 - 604

7
[ 161573-75-7 ]
[ 30506-30-0 ]
[ 64559-08-6 ]
4-bromophenyl prop-1-enyl sulfide [ No CAS ]

Reference： [1]Journal of the Chemical Society. Perkin transactions I,1999,p. 593 - 604

9
[ 30506-30-0 ]
[ 145349-76-4 ]

Reference： [1]Journal of Organic Chemistry,2001,vol. 66,p. 2104 - 2117

10
[ 64-67-5 ]
[ 106-53-6 ]
[ 30506-30-0 ]

Reference： [1]Journal of Organic Chemistry,2001,vol. 66,p. 2104 - 2117

11
[ 622-38-8 ]
ethylphenylsulfoxide [ No CAS ]
[ 30506-30-0 ]

Reference： [1]Journal of Organic Chemistry,2001,vol. 66,p. 3232 - 3234

12
[ 30506-29-7 ]
[ 30506-30-0 ]

Reference： [1]Tetrahedron Letters,2004,vol. 45,p. 5193 - 5195

13
[ 75-03-6 ]
[ 106-53-6 ]
[ 30506-30-0 ]

Yield	Reaction Conditions	Operation in experiment
93%	With caesium carbonate; In N,N-dimethyl-formamide; at 20℃; for 12h;	4-Bromobenzenethiol (0.3g, 1.59 mmol, 1.0 equiv) was dissolved in N, N-dimethylformamide (6 mL). Cs2CO3 (1.55 g, 4.76 mmol, 3.0 equiv), lodoethane (0.15 mL, 1.9 mmol, 1.2 equiv) were added and the reaction mixture was stirred at room temperature for 12 hours. The reaction mixture was diluted with water and extracted with EtOAc. The organic layer was washed with brine, dried over sodium sulfate and concentrated to afford a crude residue. The crude residue was purified by silica gel column chromatography (0-5 % EtOAc/Hexane) to afford the desired product 5.18a (0.32 g, 93 % yield). 1H NMR (400 MHz, DMSO) 6 7.50 (d, J = 8.6 Hz, 2H), 7.26 (d, J = 8.6 Hz, 2H), 2.99 (q, J = 7.3 Hz, 2H), 1.23 (t, J = 7.3 Hz, 3H).
88%	With sodium hydride; In N,N-dimethyl-formamide; mineral oil; at 20℃; for 18h;	To a solution of 4-bromobenzenethiol (6, 0.35 g, 1.85 mmol) in DMF (2 mL) was added sodium hydride (0.111 g, 60% dispersion in mineral oil, 2.77 mmol) followed by iodoethane (0.58 g, 3.7 mmol) and the mixture stirred for 18 h at r.t. The reaction mixture was diluted with water (40 mL) and extracted with EtOAc (2 x 50 mL). The combined organic extracts were dried over MgSO4, filtered, and concentrated. Purification of the resultant residue by column chromatography (eluant 5% EtOAc in hexanes) provided the title compound (0.356 g, 88% yield) as a colorless oil. 1H NMR (400 MHz, CDCl3) ppm 1.28 (t, J = 7.5 Hz, 3H), 2.89 (q, J = 7.5 Hz, 2H), 7.11-7.19 (m, 2H), 7.33-7.40 (m, 2H).

Reference： [1]Patent: WO2015/66413,2015,A1 .Location in patent: Page/Page column 174; 175
[2]Bioorganic and Medicinal Chemistry Letters,2012,vol. 22,p. 71 - 75
[3]Molecular Crystals and Liquid Crystals,2004,vol. 411,p. 93/[1135]-102/[1144]

14
[ 30506-30-0 ]
[ 115-19-5 ]
4-(4-ethylsulfanyl-phenyl)-2-methyl-but-3-yn-2-ol [ No CAS ]

Reference： [1]Molecular Crystals and Liquid Crystals,2004,vol. 411,p. 93/[1135]-102/[1144]

15
[ 30506-30-0 ]
1-ethylsulfanyl-4-ethynyl-benzene [ No CAS ]

Reference： [1]Molecular Crystals and Liquid Crystals,2004,vol. 411,p. 93/[1135]-102/[1144]

16
[ 30506-30-0 ]
4-(4-ethylsulfanyl-phenylethynyl)-2,6-difluoro-phenylamine [ No CAS ]

Reference： [1]Molecular Crystals and Liquid Crystals,2004,vol. 411,p. 93/[1135]-102/[1144]

17
[ 30506-30-0 ]
5-(4-Ethylsulfanyl-phenylethynyl)-1,3-difluoro-2-isothiocyanato-benzene [ No CAS ]

Reference： [1]Molecular Crystals and Liquid Crystals,2004,vol. 411,p. 93/[1135]-102/[1144]

18
[ 30506-30-0 ]
3,5-bis(4-thioethoxyphenyl)-1-acetophenone [ No CAS ]

Reference： [1]Journal of Organic Chemistry,2001,vol. 66,p. 2104 - 2117

19
[ 75168-73-9 ]
[ 30506-30-0 ]

Reference： [1]Journal of the Chemical Society. Perkin transactions I,1999,p. 593 - 604
[2]Journal of the Chemical Society. Chemical communications,1994,p. 805 - 806

20
FeCl₃ *6H₂O [ No CAS ]
[ 30506-30-0 ]
[ 151426-22-1 ]
[ 917382-51-5 ]

Yield	Reaction Conditions	Operation in experiment
73%	With hydrogen sulfide;	(a) bis(4-ethylthiophenyl)disulfide 18.50 g of the target compound in the form an orange oily substance was obtained, according to the same method as Example 1-(a), by reacting 4-ethylthiophenyl magnesium bromide prepared from 4.01 g (165 mmol) of magnesium metal and 32.57 g (150 mmol) of 4-ethylthiophenyl bromide with 5.29 g (165 mmol) of crystalline sulfur, oxidizing the reaction product with 40.55 g (150 mmol) of FeCl3 *6H2O, and purifying the product with column chromatography (developing solvent: ethyl acetate: n-hexane=5:95). Yield: 73% 1 H-NMR (CDCl3) [ppm]:δ1.30 (t,J=7 Hz,6H), 2.92 (q,J=7 Hz,4H), 7.13-7.30 (m, 4H), 7.32-7.49 (m, 4H)

Reference： [1]Patent: US5527940,1996,A

21
[ 30506-30-0 ]
[ 26732-20-7 ]

Yield	Reaction Conditions	Operation in experiment
91%	With 3-chloro-benzenecarboperoxoic acid; In dichloromethane; at 20℃; for 4h;	To a solution of 7b (0.35 g, 1.612 mmol) in DCM (2 mL) was added 3-chloroperoxybenzoic acid (0.7948 g, 77% w/v, 3.546 mmol). The resulting mixture was stirred for 4 h at r.t. The reaction mixture was then basified with 1 N NaOH (5 mL) and extracted with EtOAc (3 x 20 mL). The combined organic extracts were dried over MgSO4, filtered, and concentrated. The resultant residue was purified by column chromatography (eluant 15% EtOAc in hexanes) to afford the title compound (0.362 g, 91% yield) as a colorless oil. 1H NMR (400 MHz, CDCl3) δ ppm 1.27 (t, J = 7.4 Hz, 3H), 3.13 (q, J = 7.4 Hz, 2H), 7.72 (d, J = 8.6 Hz, 2H), 7.78 (d, J = 8.8 Hz, 2H).
90%	With Oxone; In water; acetonitrile; at 20℃; for 1h;	[00155] To a solution of (4-bromophenyl) (ethyl) sulfane (5 g, 23.15 mmol) in acetonitrile (50 mL) was added water (50 mL) and oxone (28.94 g, 46.30 mmol). The mixture was stirred at rt for 1 h. TLC (petroleum ethenethyl acetate = 10: 1) showed that the starting material was completely consumed. The reaction mixture was quenched with saturated aqueous sodium sulfite (150 mL) and extracted with EtOAc (3 X 50 mL). The combined organic layers were washed with water (100 mL), dried over anhydrous Na2S04, filtered and concentrated under reduced pressure. The residue was purified by silica gel chromatography eluting with petroleum ethenethyl acetate 10: 1 to 2: 1 to afford l-bromo-4-(ethylsulfonyl)benzene (5.2 g, 90%) as a white solid. 1H NMR (CDC13, 400 MHz): δ 1.13 (dd, J = 8.4, 18.0 Hz, 4H), 3.10 (q, J = 7.2 Hz, 2H), 1.26 (t, J = 7.2 Hz, 3H).
90%	With Oxone; In water; acetonitrile; at 20℃; for 1h;	To a solution of <strong>[30506-30-0](4-bromophenyl)(ethyl)sulfane</strong> (5 g, 23.15 mmol) in acetonitrile (50 mE) was added water (50 mE) and oxone (28.94 g, 46.30 mmol). The mixture was stirred at it for 1 h. TEC (petroleum ether:ethyl acetate=10:1) showed that the starting material was completely consumed. The reaction mixture was quenched with saturated aqueous sodium sulfite (150 mE) and extracted with EtOAc (3x50 mE). The combined organic layers were washed withwater (100 mE), dried over anhydrous Na2504, filtered and concentrated under reduced pressure. The residue was purified by silica gel chromatography eluting with petroleum ether:ethyl acetate 10:1 to 2:1 to afford 1 -bromo-4-(ethyl- sulfonyl)benzene (5.2 g, 90%) as a white solid. ‘H NMR (CDC13, 400 MHz): ö 7.73 (dd, J=8.4, 18.0 Hz, 4H), 3.10 (q, J=7.2 Hz, 2H), 1.26 (t, J=7.2 Hz, 3H).

	With potassium permanganate; In water; acetic acid; at 90℃; for 3h;	1-Bromo-4-ethylsulfanyl-benzene (5.0 g) was dissolved in acetic acid and potassium permanganate as a 3% solution in water (8 mL) was added. The reaction mixture was heated to 90C for 3hrs, after which time the reaction was cooled to room temperature and partitioned between ethyl acetate and 2N NaOH solution (500 m) each. The organics were separated and washed with water (100 ml), dried over sodium sulfate and purified on biotage eluting with 90:10 hexanes : ethyl acetate to afford the title compound as a clear oil (2.70 g). 1H NMR (300MHz, CDCI3): 5 1.30 (t, J=7.85 Hz, 3 H) 3.02 (q, J=7.54 Hz, 2 H), 7.40 (m, 4 H).
	With potassium monopersulfate triple salt; In methanol; water; at 20℃; for 72h;	Compound 71B: 1-bromo-4-(ethylsulfonyl)benzene Referring to the scheme above, to a solution of Oxone (4.16 g, 6.74 mmol) in H2O (30 mL) was added a solution of 71A (1.0 g, 4.49 mmol) in MeOH (15 mL). The mixture was stirred at r.t. for 3 days. The mixture was concentrated, extracted with ethyl acetate, washed with water, dried over MgSO4, and concentrated under reduced pressure to give compound 71B (985 mg). [M+H] calc'd for C8HgBrO2S 249.0; found, 249.1.

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2012,vol. 22,p. 71 - 75
[2]Patent: WO2016/61160,2016,A1 .Location in patent: Paragraph 00155
[3]Patent: US9481674,2016,B1 .Location in patent: Page/Page column 49; 50
[4]Patent: WO2006/18725,2006,A1 .Location in patent: Page/Page column 149
[5]Patent: US2007/213349,2007,A1 .Location in patent: Page/Page column 70; 71

22
[ 5533-04-0 ]
[ 30506-30-0 ]
ammonium chloride [ No CAS ]
[ 87413-09-0 ]
[ 79-22-1 ]
[ 360775-83-3 ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogenchloride; sodium hydroxide; sodium borohydrid; p-toluenesulfonic acid monohydrate; magnesium; triethylamine;iodine; In tetrahydrofuran; methanol; diethyl ether; dichloromethane; water;	Reference Example 13 2-(4-Ethylthiobenzyl)phenol A Grignard reagent was prepared from 1-bromo-4-(ethylthio)benzene (1.1g), magnesium (0.12g), a catalytic amount of iodine and tetrahydrofuran (5mL). To the Grignard reagent solution was added a solution of 2-(methoxymethoxy)-benzaldehyde (0.56g) in tetrahydrofuran (12mL), and the mixture was stirred at 65C for 10 minutes. After cooling to ambient temperature, a saturated aqueous ammonium chloride solution (5mL) and water (20mL) were added to the reaction mixture, and the mixture was extracted with ethyl acetate (80mL). The extract was washed with water (20mL) and brine (20mL), dried over anhydrous sodium sulfate, then the solvent was removed under reduced pressure. The residue was purified by column chromatography on silica gel (eluent: hexane/ethyl acetate = 4/1) to give a diphenylmethanol compound (0.91g). The obtained diphenylmethanol compound (0.90g) was dissolved in dichloromethane (15mL). To the solution was added a Dess-Martin reagent (1,1,1-tri(acetyloxy)-1,1-dihydro-1,2-benziodoxol-3(1H)-one) (1.5g), and the mixture was stirred at 25C for 26 hours. To the reaction mixture were added diethyl ether (75mL) and 1mol/L aqueous sodium hydroxide solution (30mL), the mixture was stirred vigorously, and the organic layer was separated. The organic layer was washed with 1mol/L aqueous sodiumhydroxide solution (30mL), water (30mL, 3 times) and brine (30mL), dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was purified by column chromatography on silica gel (eluent: hexane/ethyl acetate = 15/1-9/1) to afford a ketone compound (0.82g). A mixture of the obtained ketone compound (0.81g), p-toluenesulfonic acid monohydrate (0.10g) and methanol (14mL) was stirred at 60C for 4 hours. After cooling to ambient temperature, the reaction mixture was concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (eluent: hexane/ethyl acetate = 15/1) to give a deprotected compound (0.69g). The obtained deprotected compound (0.68g) was dissolved in tetrahydrofuran (11mL), triethylamine (0.41mL) and methyl chloroformate (0.22mL) were added to the solution, and the mixture was stirred at 25C for 1 hour. Furthermore, triethylamine (0.11mL) and methyl chloroformate (0.061mL) were added to the reaction mixture, and the mixture was stirred for 30 minutes. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure. The residue was dissolved in tetrahydrofuran (14mL) and water (7mL), sodium borohydride (0.40g) was added to the solution, and the mixture was stirred at 25C for 7 hours. To the reaction mixture was added dropwise 1mol/L hydrochloric acid (15mL), and the mixture was extracted with ethyl acetate (75mL). The extract was washed with water (20mL), a saturated aqueous sodium hydrogen carbonate solution (20mL) and brine (20mL), dried overanhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was purified by column chromatography on silica gel (eluent: hexane/ethyl acetate = 8/1) to give 2-(4-ethylthiobenzyl)phenol (0.62g). 1H-NMR (CDCl3) δ ppm: 1.29 (3H, t, J=7.3Hz), 2.90 (2H, q, J=7.3Hz), 3.96 (2H, s), 4.62 (1H, s), 6.75-6.80 (1H, m), 6.85-6.95 (1H, m), 7.05-7.20 (4H, m), 7.20-7.30 (2H, m)

Reference： [1]Patent: EP1270584,2003,A1

23
[ 30506-30-0 ]
[ 7439-95-4 ]
[ 917382-51-5 ]

Yield	Reaction Conditions	Operation in experiment
	With ethylene dibromide; In tetrahydrofuran; at 50℃; for 1.5h;Heating / reflux;	l-Bromo-4-(ethylthio)benzene (0.5 g, 2.3 mmol) was added to a stirred mixture of magnesium turnings (1.96g, 82mmol) in THF (1OmL). 1,2-Dibromoethane (30 μL) was then added and the mixture was heated at reflux to initiate the reaction. A solution of l-bromo-4-(ethylthio)benzene (18.2 g, 84 mmol) in THF (60 mL) was added at such a rate to maintain the reaction mixture at gentle reflux. The reaction mixture was then stirred at 5O0C for 90 min and cooled to ambient temp to give a 1.16M solution of 4- (ethylthio)phenylmagnesium bromide in THF which was used in the next reaction.

Reference： [1]Patent: WO2006/134341,2006,A1 .Location in patent: Page/Page column 41

24
aqueous ammonium chloride [ No CAS ]
[ 5533-04-0 ]
[ 30506-30-0 ]
[ 6192-52-5 ]
[ 87413-09-0 ]
[ 79-22-1 ]
[ 360775-83-3 ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogenchloride; aqueous sodium hydroxide; sodium borohydrid; magnesium; triethylamine;iodine; In tetrahydrofuran; methanol; diethyl ether; dichloromethane; water;	Reference Example 4 2-(4-Ethylthiobenzyl)phenol A Grignard reagent was prepared from 1-bromo-4-ethyl-thiobenzene (1.1 g), magnesium (0.12 g), a catalytic amount of iodine and tetrahydrofuran (5 mL) in the usual manner. To the obtained Grignard reagent solution was added a solution of 2-(methoxymethoxy)benzaldehyde (0.56 g) in tetrahydrofuran (12 mL), and the mixture was stirred at 65 C. for 10 minutes. After cooling to ambient temperature, a saturated aqueous ammonium chloride solution (5 mL) and water (20 mL) were added to the reaction mixture, and the mixture was extracted with ethyl acetate (80 mL). The extract was washed with water (20 mL) and brine (20 mL), dried over anhydrous sodium sulfate, then the solvent was removed under reduced pressure. The residue was purified by column chromatography on silica gel (eluent: hexane/ethyl acetate=4/1) to give a diphenylmethanol compound (0.91 g). The obtained diphenylmethanol compound (0.90 g) was dissolved in dichloromethane (15 mL). To the solution was added a Dess-Martin reagent (1,1,1-tris(acetyloxy)-1,1-dihydro-1,2-benziodoxol-3-(1H)-one) (1.5 g), and the mixture was stirred at 25 C. for 26 hours. To the reaction mixture were added diethyl ether (75 mL) and 1 mol/L aqueous sodium hydroxide solution (30 mL), the mixture was stirred vigorously, and the organic layer was separated. The organic layer was washed with 1 mol/L aqueous sodium hydroxide solution (30 mL), water (30 mL, 3 times) and brine (30 mL), dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was purified by column chromatography on silica gel (eluent: hexane/ethyl acetate=15/1-9/1) to afford a ketone compound (0.82 g). A mixture of the obtained ketone compound (0.81 g), p-toluene-sulfonic acid monohydrate (0.10 g) and methanol (14 mL) was stirred at 60 C. for 4 hours. After cooling to ambient temperature, the reaction mixture was concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (eluent: hexane/ethyl acetate=15/1) to give a deprotected compound (0.69 g). The obtained deprotected compound (0.68 g) was dissolved in tetrahydrofuran (11 mL), triethylamine (0.41 mL) and methyl chloroformate (0.22 mL) were added to the solution, and the mixture was stirred at 25 C. for 1 hour. Furthermore, triethylamine (0.1 mL) and methyl chloroformate (0.061 mL) were added to the reaction mixture, and the mixture was stirred for 30 minutes. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure. The residue was dissolved in tetrahydrofuran (14 mL) and water (7 mL), sodium borohydride (0.40 g) was added to the solution, and the mixture was stirred at 25 C. for 7-hours. To the reaction mixture was added dropwise 1 mol/L hydrochloric acid (15 mL), and the mixture was extracted with ethyl acetate (75 mL). The extract was washed with water (20 mL), a saturated aqueous sodium hydrogen carbonate solution (20 mL) and brine (20 mL), dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was purified by column chromatography on silica gel (eluent: hexane/ethyl acetate=8/1) to give 2-(4-ethyl-thiobenzyl)phenol (0.62 g). 1H-NMR (CDCl3) δ ppm: 1.29 (3H, t, J=7.3 Hz), 2.90 (2H, q, J=7.3 Hz), 3.96 (2H, s), 4.62 (1H, s), 6.75-6.80 (1H, m), 6.85-6.95 (1H, m), 7.05-7.20 (4H, m), 7.20-7.30 (2H, m)

Reference： [1]Patent: US2004/18998,2004,A1

25
[ 30506-30-0 ]
[ 50373-10-9 ]
[ 1186233-79-3 ]

Reference： [1]Bioorganic and Medicinal Chemistry,2009,vol. 17,p. 5126 - 5132

26
[ 30506-30-0 ]
[ 1066-45-1 ]
[ 874910-40-4 ]

Yield	Reaction Conditions	Operation in experiment
65.01%		(S)-4-Ethylsulfonyl benzoylalaninePreparation 1. Synthesis of trimethyl-4-(ethyIthio-phenyl) stannaneA solution of 1-bromo-4-ethylthio benzene (3.1 g, 13.82 mmoles) in anhydrous THF (42.09 ml) is added with 2.5 eq of 1.6 M tBuLi in pentane (21.4 ml), under magnetic stirring and argon inert atmosphere, at -78C. The mixture turns yellow. The mixture is reacted at -78C for an hour, then added with 2.18 eq of a 1M solution of Me3SnCl in THF (30.13 ml), under the same conditions as above, then it is slowly cooled to room temperature and reacted under these conditions for 3 hrs, monitoring the progress of the reaction byTLC (petroleum etherrEtOAc = 8:2) in which the stannylation product shows Rf higher than the starting bromo-derivative. The mixture is subsequently poured onto ice and extracted with AcOEt. The organic phase is dried over dry Na2SO4, filtered through paper filter and concentrated in rotary evaporator. The residue is purified by flash chromatography on silica gel, eluting with petroleum ether. 2.78 g of a clear pale yellow oil are obtained. Yield: 65.01%.'H-NMR (CDC13, 200 MHz) 6: 0.36 (s, 9H, (CHO.Sn); 1.39 (t, 3H, J - 5.34, CH3_CH2S); 3.01 (q, 2H, J, = 7.38 Hz, J2 = 14.7 Hz, CH,CHZS); 3-5-7.6 (2m, 4H, Ar).IR (CHC13); 3059.03; 2972.73; 2925.97; 4868.56; 1885.56; 1631.48; 1566,4; 1471.42; 1447.31; 1386.09; 1264.59; 1180.22; 1111.28; 1091.99; 1068.85; 1005.21; 969.055.

Reference： [1]Patent: WO2006/13085,2006,A1 .Location in patent: Page/Page column 3-4

27
[ 30506-30-0 ]
[ 1021169-18-5 ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2012,vol. 22,p. 71 - 75

28
[ 30506-30-0 ]
[ 26732-20-7 ]
[ 363136-57-6 ]
(S)-1-bromo-4-(ethylsulfinyl)benzene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With titanium(IV) isopropylate; tert.-butylhydroperoxide; 2-benzyl-1,3-diphenylpropane-1,3-diol; In toluene; at -20℃; for 36h;Molecular sieve;	General procedure: To a solution 1,3-diol (16 mg, 0.05 mmol) containing MS4Å (70 mg) was added Ti(O-iPr)4 (7.4 μL, 0.025 mmol) in toluene (1 mL). The mixture was stirred for 2 h at rt and then methyl(p-tolyl)sulfane (68 μL, 0.5 mmol) was added. The mixture was cooled to -20 C and t-butylhydroperoxide (0.16 mL, 0.8 mmol)18 was added. After stirring for 36 h at the same temperature, the reaction was quenched with 10% aqueous solution of sodium sulfite. The aqueous layer was extracted with ethyl acetate (3 × 15 mL) and organic layer was dried (Na2SO4). The solvent was evaporated under reduced pressure to leave the crude product, which was separated by preparative TLC (3:2; hexane/ethyl acetate) to give 8g (46 mg, 60%). The product was characterised by spectroscopic analysis and the analyses were consistent with the literature. Enantiomeric excess was determined by chiral HPLC on a Chiralcel OD-H (250 × 4.6 mm) column eluting with a hexane/isopropanol (9:1) mixture (1 mL/min, λ = 250 nm).

Reference： [1]Tetrahedron Letters,2012,vol. 53,p. 2726 - 2729

29
[ 30506-30-0 ]
[ 120329-58-0 ]
6,9,12,15,18-pentakis(4'-ethylthiophenyl)-1-hydro[60]fullerene [ No CAS ]

Reference： [1]Chemistry - A European Journal,2012,vol. 18,p. 7418 - 7433

30
[ 30506-30-0 ]
(S)-α,α-bis(4-ethylphenylthio)-2-pyrrolidinemethanol trimethylsilylether [ No CAS ]

Reference： [1]European Journal of Organic Chemistry,2013,p. 5917 - 5922

31
[ 30506-30-0 ]
[ 59936-29-7 ]
C₂₆H₃₅NO₃S₂ [ No CAS ]

Reference： [1]European Journal of Organic Chemistry,2013,p. 5917 - 5922

32
[ 30506-30-0 ]
[ 274-79-3 ]
[ 1606131-44-5 ]

Reference： [1]European Journal of Organic Chemistry,2014,vol. 2014,p. 1589 - 1593
[2]European Journal of Organic Chemistry,2014,vol. 2014,p. 1589 - 1593

33
[ 30506-30-0 ]
[ 1606131-66-1 ]

Reference： [1]European Journal of Organic Chemistry,2014,vol. 2014,p. 1589 - 1593
[2]European Journal of Organic Chemistry,2014,vol. 2014,p. 1589 - 1593

34
[ 30506-30-0 ]
[ 1606131-67-2 ]

Reference： [1]European Journal of Organic Chemistry,2014,vol. 2014,p. 1589 - 1593
[2]European Journal of Organic Chemistry,2014,vol. 2014,p. 1589 - 1593

35
[ 30506-30-0 ]
[ 1606131-68-3 ]

Reference： [1]European Journal of Organic Chemistry,2014,vol. 2014,p. 1589 - 1593
[2]European Journal of Organic Chemistry,2014,vol. 2014,p. 1589 - 1593

36
[ 30506-30-0 ]
[ 26732-20-7 ]
[ 30506-29-7 ]

Reference： [1]Organic and Biomolecular Chemistry,2021,vol. 19,p. 156 - 161
[2]Inorganic Chemistry,2016,vol. 55,p. 2701 - 2708

37
[ 30506-30-0 ]
[ 393536-19-1 ]
(R)-N-((R)-2-((tert-butyldimethylsilyl)oxy)-1-(4-(ethylthio)phenyl)ethyl)-2-methylpropane-2-sulfinamide [ No CAS ]
(R)-N-((S)-2-((tert-butyldimethylsilyl)oxy)-1-(4-(ethylthio)phenyl)ethyl)-2-methylpropane-2-sulfinamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		To a solution of <strong>[30506-30-0](4-bromophenyl)(ethyl)sulfane</strong> (1.88 g, 8.65 mmol) in anhydrous THF (15 mL) was added n-BuLi (14.4 mL, 36.0 mmol, 2.5 M in THF) at -78 C. under N2. The reaction mixture was stirred at -78 C. for 0.5 h, then a solution of (R,E)-N-(2-((tert-butyldimethylsilyl)oxy)ethylidene)-2-methylpropane-2-sulfinamide (2.0 g, 7.2 mmol) in THF (1 mL) was added dropwise to the mixture at -78 C. The reaction mixture was stirred at -78 C. for 0.5 h and was allowed to warm to rt. After 0.5 h at rt, the reaction mixture was quenched with water (10 mL) and extracted with ethyl acetate (3×20 mL). The combined organic layers were washed with H2O (10 mL) then brine (10 mL), dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The crude residue was purified by column chromatography on silica gel (eluting with a gradient of 5% to 10% ethyl acetate in petroleum ether) to afford a 3:2 mixture of (R)-N-((R)-2-((tert-butyldimethylsilyl)oxy)-1-(4-(ethylthio)phenyl)ethyl)-2-methylpropane-2-sulfinamide and (R)-N-((S)-2-((tert-butyldimethylsilyl)oxy)-1-(4-(ethylthio)phenyl)ethyl)-2-methylpropane-2-sulfinamide (2.86 g, 47.9%) as a yellow oil. This 3:2 mixture of diastereomers was used for the subsequent reactions. 1H NMR (CDCl3 400 MHz): δ 7.24-7.16 (m, 4H), 4.47-4.40 (m, 1H), 4.21 (s, 1H), 3.75-3.67 (m, 1H), 3.60-3.47 (m, 1H), 2.90 (q, J=7.2 Hz, 2H), 1.27 (t, J=7.2 Hz, 3H), 1.18 (s, 9H), 0.85 (s, 9H), 0.02 (s, 3H), 0.00 (s, 3H).
		To a solution of <strong>[30506-30-0](4-bromophenyl)(ethyl)sulfane</strong> (1.88 g, 8.65 mmol) in anhydrous THF (15 mL) was added n-BuLi (14.4 mL, 36.0 mmol, 2.5 M in THF) at -78 C under N2. The reaction mixture was stirred at -78 C for 0.5 h, then a solution of (R,E)-N-(2-((tert- butyldimethylsilyl)oxy)ethylidene)-2-methylpropane-2-sulfinamide (2.0 g, 7.2 mmol) in THF (1 mL) was added dropwise to the mixture at -78 C. The reaction mixture was stirred at -78 C for 0.5 h and was allowed to warm to rt. After 0.5 h at rt, the reaction mixture was quenched with water (10 mL) and extracted with ethyl acetate (3 x 20 mL). The combined organic layers were washed with H2O (10 mL) then brine (10 mL), dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The crude residue was purified by column chromatography on silica gel (eluting with a gradient of 5% to 10% ethyl acetate in petroleum ether) to afford a 3:2 mixture of (R)-N-((R)-2-((tert-butyldimethylsilyl)oxy)-1-(4-(ethylthio)phenyl)ethyl)-2-methylpropane-2-sulfinamide and (R)-N-((S)-2-((tert-butyldimethylsilyl)oxy)-1-(4-(ethylthio)phenyl)ethyl)-2-methylpropane-2-sulfinamide (2.86 g, 47.9 %) as a yellow oil. This 3:2 mixture of diastereomers was used for the subsequent reactions. 1H NMR (CDCl3 400 MHz): δ 7.24-7.16 (m, 4H), 4.47-4.40 (m, 1H), 4.21 (s, 1H), 3.75-3.67 (m, 1H), 3.60-3.47 (m, 1H), 2.90 (q, J = 7.2 Hz, 2H), 1.27 (t, J = 7.2 Hz, 3H), 1.18 (s, 9H), 0.85 (s, 9H), 0.02 (s, 3H), 0.00 (s, 3H).

Reference： [1]Patent: US2016/122318,2016,A1 .Location in patent: Paragraph 0184-0185
[2]Patent: WO2017/24018,2017,A1 .Location in patent: Paragraph 00133; 00134

38
[ 30506-30-0 ]
(R)-2-amino-2-(4-(ethylthio)phenyl)ethan-1-ol hydrochloride [ No CAS ]

Reference： [1]Patent: WO2016/61160,2016,A1
[2]Patent: WO2017/132432,2017,A1

39
[ 30506-30-0 ]
(R)-2-amino-2-(4-(ethylsulfonyl)phenyl)ethan-1-ol [ No CAS ]

Reference： [1]Patent: WO2016/61160,2016,A1
[2]Patent: US2016/122345,2016,A1
[3]Patent: WO2017/87608,2017,A1
[4]Patent: WO2017/132432,2017,A1

40
[ 30506-30-0 ]
(E)-1-(ethylsulfonyl)-4-(prop-1-en-1-yl)benzene [ No CAS ]

Reference： [1]Patent: WO2016/61160,2016,A1
[2]Patent: US9481674,2016,B1

41
[ 30506-30-0 ]
tert-butyl ((1R,2R)-1-(4-(ethylsulfonyl)phenyl)-2-hydroxypropyl)carbamate [ No CAS ]
tert-butyl ((1S,2S)-1-(4-(ethylsulfonyl)phenyl)-2-hydroxypropyl)carbamate [ No CAS ]

Reference： [1]Patent: WO2016/61160,2016,A1
[2]Patent: US9481674,2016,B1

42
[ 30506-30-0 ]
(1R,2R)-1-amino-1-(4-(ethylsulfonyl)phenyl)propan-2-ol [ No CAS ]
(1S,2S)-1-amino-1-(4-(ethylsulfonyl)phenyl)propan-2-ol [ No CAS ]

Reference： [1]Patent: WO2016/61160,2016,A1

43
[ 30506-30-0 ]
(2S,3S)-2-(4-(ethylsulfonyl)phenyl)-3-methyloxirane [ No CAS ]
(2R,3R)-2-(4-(ethylsulfonyl)phenyl)-3-methyloxirane [ No CAS ]

Reference： [1]Patent: WO2016/61160,2016,A1
[2]Patent: US9481674,2016,B1

44
[ 30506-30-0 ]
(1R,2S)-1-amino-1-(4-(ethylsulfonyl)phenyl)propan-2-ol [ No CAS ]
(1S,2R)-1-amino-1-(4-(ethylsulfonyl)phenyl)propan-2-ol [ No CAS ]

Reference： [1]Patent: WO2016/61160,2016,A1
[2]Patent: US9481674,2016,B1

45
[ 30506-30-0 ]
(S)-tert-butyl 3-(((R)-1-(4-(ethylsulfonyl)phenyl)-2-hydroxyethyl)carbamoyl)-7-isopropyl-5H-pyrrolo[3,4-b]pyridine-6(7H)-carboxylate [ No CAS ]

Reference： [1]Patent: WO2016/61160,2016,A1

46
[ 30506-30-0 ]
(S)-N-((R)-1-(4-(ethylsulfonyl)phenyl)-2-hydroxyethyl)-7-isopropyl-6,7-dihydro-5H-pyrrolo[3,4-b]pyridine-3-carboxamide [ No CAS ]

Reference： [1]Patent: WO2016/61160,2016,A1

47
[ 30506-30-0 ]
(S)-N-((R)-1-(4-(ethylsulfonyl)phenyl)-2-hydroxyethyl)-7-isopropyl-6-((trans-4-(trifluoromethyl)cyclohexyl)methyl)-6,7-dihydro-5H-pyrrolo[3,4-b]pyridine-3-carboxamide [ No CAS ]

Reference： [1]Patent: WO2016/61160,2016,A1

48
[ 30506-30-0 ]
(S)-tert-butyl 7-ethyl-3-(((R)-1-(4-(ethylsulfonyl)phenyl)-2-hydroxyethyl)carbamoyl)-5H-pyrrolo[3,4-b]pyridine-6(7H)-carboxylate [ No CAS ]

Reference： [1]Patent: WO2016/61160,2016,A1
[2]Patent: US2016/122345,2016,A1

49
[ 30506-30-0 ]
(S)-7-ethyl-N-((R)-1-(4-(ethylsulfonyl)phenyl)-2-hydroxyethyl)-6,7-dihydro-5H-pyrrolo[3,4-b]pyridine-3-carboxamide [ No CAS ]

Reference： [1]Patent: WO2016/61160,2016,A1

50
[ 30506-30-0 ]
(S)-7-ethyl-N-((R)-1-(4-(ethylsulfonyl)phenyl)-2-hydroxyethyl)-6-((trans-4-(trifluoromethyl)cyclohexyl)methyl)-6,7-dihydro-5H-pyrrolo[3,4-b]pyridine-3-carboxamide hydrochloride [ No CAS ]

Reference： [1]Patent: WO2016/61160,2016,A1

51
[ 30506-30-0 ]
(S)-7-ethyl-N-((R)-1-(4-(ethylsulfonyl)phenyl)-2-hydroxyethyl)-6-((trans-4-(trifluoromethyl)cyclohexyl)methyl)-6,7-dihydro-5H-pyrrolo[3,4-b]pyridine-3-carboxamide monomesylate [ No CAS ]

Reference： [1]Patent: WO2016/61160,2016,A1

52
[ 30506-30-0 ]
[ 393536-19-1 ]
(R)-N-((R)-2-((tert-butyldimethylsilyl)oxy)-1-(4-(ethylthio)phenyl)ethyl)-2-methylpropane-2-sulfinamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
44%		[00148] To a solution of (4-bromophenyl) (ethyl) sulfane (28.9 g, 133.1 mmol) in anhydrous THF (500 mL) was added dropwise w-butyllithium (73 mL, 181.5 mmol, 2.5 M in hexanes) at -78 C. The mixture was stirred at -78 C for 30 min. A solution of (R,E)-N-(2- ((ieri-butyldimethylsilyl)oxy)ethylidene)-2-methylpropane-2-sulfinamide (33.5 g, 121 mmol) in anhydrous THF (100 mL) was added to the mixture at -78 C. The mixture was stirred at - 78 C for 2 h, then allowed to warm to rt and stirred for 2 h. The mixture was quenched with saturated aqueous NH4CI solution (200 mL) and extracted with ethyl acetate (3 x 300 mL). The combined organic layer was washed with water (200 mL) and brine (200 mL), dried over anhydrous Na2S04, filtered and concentrated under vacuum. The residue was purified by silica gel chromatography (eluting with petroleum ether: ethyl acetate = 15: 1) three times to afford (R)-N-((R)-2-((ieri-butyldimethylsilyl)oxy)- 1- (4-(ethylthio)phenyl)ethyl)-2- methylpropane-2-sulfinamide (22 g, 44%) as a yellow oil. 1H NMR (CDC13, 400 MHz): δ 7.21-7.24 (d, J = 7.2 Hz, 2H), 7.18-7.21 (d, J = 8.4 Hz, 2H), 4.42-4.45 (dd, J = 8.8, 2.4 Hz, 1H), 4.21 (brs, 1H), 3.69-3.73 (dd, J = 10.4, 4.4 Hz, 1H), 3.51-3.56 (t, J = 9.6 Hz, 1H), 2.87- 2.92 (q, J = 1.6 Hz, 2H), 1.25- 1.29 (t, J = 1.2 Hz, 3H), 1.18 (s, 9H), 0.88 (s, 9H), 0.02 (s, 6H). LCMS tR = 1.010 min in 5-95AB_1.5 min chromatography (MK RP18e 25-2mm), MS (ESI) m/z 437.9 [M+Na]+. Isomer SFC tR = 3.607 and 4.014 min in 12 min chromatography (AD- H_5_5_40_2.3 5 ML), ee = 90.85%.
44%		To a solution of <strong>[30506-30-0](4-bromophenyl)(ethyl)sulfane</strong> (28.9 g, 133.1 mmol) in anhydrous THF (500 mL) was added dropwise n-butyllithium (73 mL, 181.5 mmol, 2.5 M in hexanes) at -78 C. The mixture was stirred at -78 C. for 30 min. A solution of (R,E)-N-(2-((tert-butyldimethylsilyl)oxy)ethylidene)-2-methylpropane-2-sulfinamide (33.5 g, 121 mmol) in anhydrous THF (100 mL) was added to the mixture at -78 C. The mixture was stirred at -78 C. for 2 h, then allowed to warm to rt and stirred for 2 h. The mixture was quenched with saturated aqueous NH4Cl solution (200 mL) and extracted with ethyl acetate (3×300 mL). The combined organic layer was washed with water (200 mL) and brine (200 mL), dried over anhydrous Na2SO4, filtered and concentrated under vacuum. The residue was purified by silica gel chromatography (eluting with petroleum ether:ethyl acetate=15:1) three times to afford (R)-N-((R)-2-((tert-butyldimethylsilyl)oxy)-1-(4-(ethylthio)phenyl)ethyl)-2-methylpropane-2-sulfinamide (22 g, 44%) as a yellow oil. 1H NMR (CDCl3, 400 MHz): δ 7.21-7.24 (d, J=7.2 Hz, 2H), 7.18-7.21 (d, J=8.4 Hz, 2H), 4.42-4.45 (dd, J=8.8, 2.4 Hz, 1H), 4.21 (brs, 1H), 3.69-3.73 (dd, J=10.4, 4.4 Hz, 1H), 3.51-3.56 (t, J=9.6 Hz, 1H), 2.87-2.92 (q, J=7.6 Hz, 2H), 1.25-1.29 (t, J=7.2 Hz, 3H), 1.18 (s, 9H), 0.88 (s, 9H), 0.02 (s, 6H). LCMS tR=1.010 min in 5-95AB_1.5 min chromatography (MK RP18e 25-2 mm), MS (ESI) m/z 437.9 [M+Na]+. Isomer SFC tR=3.607 and 4.014 min in 12 min chromatography (AD-H_5_5_40_2.3 5 ML), ee=90.85%.
44%		To a solution of <strong>[30506-30-0](4-bromophenyl)(ethyl)sulfane</strong> (28.9 g,133.1 mmol) in anhydrous THF (500 mE) was addeddropwise n-butyllithium (73 mE, 181.5 mmol, 2.5 M inhexanes) at -78 C. The mixture was stirred at -78 C. for30 mm. A solution of (R,E)-N-(2-((teit-butyldimethylsilyl)oxy)ethylidene)-2-methylpropane-2-sulfinamide (33.5 g,121 mmol) in anhydrous THF (100 mE) was added to themixture at -78 C. The mixture was stirred at -78 C. for 2h, then allowed to warm to it and stirred for 2 h. The mixturewas quenched with saturated aqueous NH4C1 solution (200mE) and extracted with ethyl acetate (3x300 mE). Thecombined organic layer was washed with water (200 mE)and brine (200 mE), dried over anhydrous Na2SO4, filteredand concentrated under vacuum. The residue was purified bysilica gel chromatography (eluting with petroleum ether:ethyl acetate=1 5:1) three times to afford (R)-N-((R)-2-((teit-butyldimethylsilyl)oxy)-1 -(4-(ethylthio)phenyl)ethyl)-2-methylpropane-2-sulfinamide (22 g, 44%) as ayellow oil. ‘H NMR (CDC13, 400 MHz): ö 7.21-7.24 (d,J=7.2 Hz, 2H), 7.18-7.21 (d, J=8.4 Hz, 2H), 4.42-4.45 (dd,J=8.8, 2.4 Hz, 1H), 4.21 (brs, 1H), 3.69-3.73 (dd, J=10.4, 4.4Hz, 1H), 3.51-3.56 (t, J=9.6 Hz, 1H), 2.87-2.92 (q, J=7.6 Hz,2H), 1.25-1.29 (t, J=7.2 Hz, 3H), 1.18 (s, 9H), 0.88 (s, 9H),0.02 (s, 6H). ECMS tR=1.010 mm in 5-95A13_1.5 mm chromatography (MK RP1 8e 25-2 mm), MS (ESI) mlz 437.9 [M+Na]t Isomer SFC tR=3.607 and 4.014 mm in 12mm chromatography (AD-H_5_5_40_2.3 5 ME), ee=90.85%.

44%

[00208] To a solution of <strong>[30506-30-0](4-bromophenyl)(ethyl)sulfane</strong> (28.9 g, 133.1 mmol) in anhydrous THF (500 mL) was added dropwise n-butyllithium (73 mL, 181.5 mmol, 2.5 M in hexanes) at - 78 C. The mixture was stirred at -78 C for 30 min. A solution of (R,E)-N-(2-((tert- butyldimethylsilyl)oxy)ethylidene)-2-methylpropane-2-sulfinamide (33.5 g, 121 mmol) in anhydrous THF (100 mL) was added to the mixture at -78 C. The mixture was stirred at -78 C for 2 h, then allowed to warm to rt and stirred for 2 h. The mixture was quenched with satd aq NH4C1 solution (200 mL) and extracted with EtOAc (3 x 300 mL). The combined organic layer was washed with water (200 mL) and brine (200 mL), dried over anhydrous Na2S04, filtered and concentrated under vacuum. The residue was purified by silica gel chromatography (eluting with petroleum ether: EtOAc = 15: 1) three times to afford (R)-N-((R)-2-((tert- butyldimethylsilyl)oxy)- l- (4-(ethylthio)phenyl)ethyl)-2-methylpropane-2-sulfinamide (22 g, 44%) as a yellow oil. 1H NMR (CDCI3, 400 MHz): δ 7.21-7.24 (d, J = 1.2 Hz, 2H), 7.18-7.21 (d, J = 8.4 Hz, 2H), 4.42-4.45 (dd, J = 8.8, 2.4 Hz, 1H), 4.21 (brs, 1H), 3.69-3.73 (dd, J = 10.4, 4.4 Hz, 1H), 3.51-3.56 (t, J = 9.6 Hz, 1H), 2.87-2.92 (q, J = 7.6 Hz, 2H), 1.25-1.29 (t, J = 1.2 Hz, 3H), 1.18 (s, 9H), 0.88 (s, 9H), 0.02 (s, 6H). LC-MS Method 3 tR = 1.010 min MS (ESI) m/z 437.9 [M+Na]+. Isomer SFC tR = 3.607 and 4.014 min in 12 min chromatography (AD- H55402.3 5 ML), ee = 90.85%.

Reference： [1]Patent: WO2016/61160,2016,A1 .Location in patent: Paragraph 00148
[2]Patent: US2016/122345,2016,A1 .Location in patent: Paragraph 0115; 0120
[3]Patent: US9481674,2016,B1 .Location in patent: Page/Page column 47; 48
[4]Patent: WO2017/132432,2017,A1 .Location in patent: Paragraph 00207-00208

53
[ 30506-30-0 ]
(R)-N-((R)-1-(4-(ethylthio)phenyl)-2-hydroxyethyl)-2-methylpropane-2-sulfinamide [ No CAS ]