* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Reference：
[1] Journal of the American Chemical Society, 1982, vol. 104, # 20, p. 5412 - 5418
[2] Journal of the American Chemical Society, 1997, vol. 119, # 41, p. 9913 - 9914
[3] Organic Letters, 2003, vol. 5, # 8, p. 1317 - 1320
[4] Synthetic Communications, 2004, vol. 34, # 3, p. 501 - 507
[5] European Journal of Organic Chemistry, 2005, # 9, p. 1727 - 1730
[6] Tetrahedron Asymmetry, 2006, vol. 17, # 4, p. 508 - 511
[7] Organic Letters, 2007, vol. 9, # 7, p. 1255 - 1258
[8] Organic Letters, 2007, vol. 9, # 7, p. 1255 - 1258
[9] Journal of Organic Chemistry, 2003, vol. 68, # 1, p. 150 - 155
[10] Chemical Communications, 2006, # 13, p. 1393 - 1394
[11] Organic Syntheses, 2005, vol. 82, p. 157 - 165
2
[ 110-06-5 ]
[ 60011-16-7 ]
Yield
Reaction Conditions
Operation in experiment
92%
With bis(acetylacetonate)oxovanadium; C27H39NO2Si; dihydrogen peroxide In acetone at -5 - 0℃;
After reacting (1R,2S)-prolinol trisilyl ether with 3,5-dimethylsalicaldehyde in an equivalent amount, ligand L2 was obtained (specific process reference: Org. Synth. 2005, 82, 157). The ligand L2 (5.0 mmol) and VO(acac)2 (1.27 g, 4.8 mmol) were added to acetone and stirred for 1 hour. After the color of the system became dark, the TLC reaction was complete. T-butyl disulfideEthyl ether (169.4 g, 0.95 mol) was dissolved in 190 ml of acetone, and the temperature was controlled at -5°C to 0°C. 30percent hydrogen peroxide (1.02 mol) was slowly added dropwise. The addition was completed in about 20-22 hours, and the raw materials and products were kept warm. When the ratio reaches 90:1, it is considered as the end of the reaction. The temperature is controlled to not exceed 35°C. The solvent is distilled off under reduced pressure. 400 mL of diethoxymethane (DEM) is added for layering. The organic layer is washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solution is tested for (S)-tert-butyl sulfoxide. Acetyl tert-butyl thioester external standard yield 92percent (169.8g, 0.87mol), 96.5percent ee;
Reference：
[1] Patent: CN106478471, 2017, A, . Location in patent: Paragraph 0018; 0019
3
[ 110-06-5 ]
[ 67734-35-4 ]
[ 60011-16-7 ]
Reference：
[1] Journal of the American Chemical Society, 1982, vol. 104, # 20, p. 5412 - 5418
[2] Journal of the American Chemical Society, 1997, vol. 119, # 41, p. 9913 - 9914
[3] Organic Letters, 2003, vol. 5, # 8, p. 1317 - 1320
[4] Synthetic Communications, 2004, vol. 34, # 3, p. 501 - 507
[5] European Journal of Organic Chemistry, 2005, # 9, p. 1727 - 1730
[6] Tetrahedron Asymmetry, 2006, vol. 17, # 4, p. 508 - 511
[7] Organic Letters, 2007, vol. 9, # 7, p. 1255 - 1258
[8] Organic Letters, 2007, vol. 9, # 7, p. 1255 - 1258
[9] Journal of Organic Chemistry, 2003, vol. 68, # 1, p. 150 - 155
[10] Chemical Communications, 2006, # 13, p. 1393 - 1394
[11] Organic Syntheses, 2005, vol. 82, p. 157 - 165
4
[ 60011-16-7 ]
[ 343338-28-3 ]
Yield
Reaction Conditions
Operation in experiment
75%
at -60 - 0℃; for 1 h;
In the third step, 120 mL of diethoxymethane was added to the reaction flask, and the temperature was controlled between -60 °C and -70 °C. Liquid ammonia (23.8 g, 1.40 mol) was added dropwise to 2.6 mL of 2.3M n-hexyllithium (0.96). Molar), the solution appeared during the process of white solids, incubation reaction 0.5 hours. Then (S)-tert-butylsulfinyl tert-butyl thioester (169.8 g, 0.87 mol, 96.5percent ee) and ethyl chloride (80.4 g, 1.25 mol) were added dropwise to the diethoxymethane solution (by The product solution obtained in the second step was cooled to 0° C. and mixed with ethyl chloride). After the dropwise addition was completed, the reaction was incubated for 1 hour while the reaction was stirred and the reaction was completed. After the reaction solution was evaporated to dryness under reduced pressure, 1400 mL of methyl tert-butyl ether was added, filtered through celite, and the solvent was evaporated. 135 mL of n-heptane was slurried between -10°C and 0°C to obtain fine needle crystals. (3)-tert-butyl Sulfonamide 79.1 g, yield 75percent, HPLC: 99.7percent, 99.4percent ee.
Reference：
[1] Patent: CN106478471, 2017, A, . Location in patent: Paragraph 0018; 0019
A pre-cooled solution of <strong>[60011-16-7](S)-tert-butyl tert-butanethiosulfinate</strong> (1 equiv, 745 mg, 3.83 mmol) in THF (18.6 mL, C=0.2 mol/L) was added to a solution of phenyllithium in diethyl ether (2 equiv, 7.66 mmol) at -78 C. After 2 h at -78 C, water was added (10 mL). The layers were separated and the aqueous layer was extracted with dichloromethane (2*10 mL). The combined organic layers were dried over Na2SO4, filtered and evaporated to dryness. The crude product was purified by column chromatography on silica gel (eluent: cyclohexane/AcOEt 7/3) to afford (S)-(tert-butyl sulfinyl)benzene 1d as a colorless solid (587 mg, 3.22 mmol, 84%). 1H NMR (CDCl3, 300 MHz): delta=7.54-7.51 (m, 2H), 7.43-7.41 (m, 3H),1.10 (s, 9H, CMe3) ppm. 13C NMR (CDCl3, 75 MHz): delta=140.1 (CIV, CS(O)CMe3), 131.1, 128.3 (2C), 126.3 (2C), 55.8 (C4, CMe3), 22.9 (CMe3) ppm. HRMS (ESI) [M+Na]+ for C10H14OSNa calcd 205.0658, found 205.0655.[a]D20=-171.5 (c 1, CHCl3). Mp 87-89 C. [*Phenyllithium was prepared by adding tert-butyllithium (1.7 M in pentane, 2.0 equiv) to iodobenzene (1 equiv) in diethyl ether (4 mL/mmol iodobenzene) and stirring for 30 min at -78 C. The absence of tert-butyllithium was veried by means of a Gilman test II reaction.]24
The first step is the cryogenic Grignard addition of the commercially available 3-bromo-1,1-dimethoxy propane and the known <strong>[60011-16-7](S)-S-tert-butyl 2-methylpropane-2-sulfinothioate</strong>.The identity of the in situ generated organometallic reagent could be comprised of eitherthe Mg, Li, Zn, Cu, In, or Sm species. The reaction is conducted by separately generatingthe organometallic reagent followed by addition of the thiosulfinate as a solution in THF(tetrahydrofuran). This addition mode acts to assist in the prevention of thiosulfinate racemization. This addition results in the inversion of stereochemistry at the sulfur stereocenter, and the generation of compound la (75-85% yield).
With ammonia; n-hexyllithium; at -60 - 0℃; for 1h;
In the third step, 120 mL of diethoxymethane was added to the reaction flask, and the temperature was controlled between -60 C and -70 C. Liquid ammonia (23.8 g, 1.40 mol) was added dropwise to 2.6 mL of 2.3M n-hexyllithium (0.96). Molar), the solution appeared during the process of white solids, incubation reaction 0.5 hours. Then (S)-tert-butylsulfinyl tert-butyl thioester (169.8 g, 0.87 mol, 96.5% ee) and ethyl chloride (80.4 g, 1.25 mol) were added dropwise to the diethoxymethane solution (by The product solution obtained in the second step was cooled to 0 C. and mixed with ethyl chloride). After the dropwise addition was completed, the reaction was incubated for 1 hour while the reaction was stirred and the reaction was completed. After the reaction solution was evaporated to dryness under reduced pressure, 1400 mL of methyl tert-butyl ether was added, filtered through celite, and the solvent was evaporated. 135 mL of n-heptane was slurried between -10C and 0C to obtain fine needle crystals. (3)-tert-butyl Sulfonamide 79.1 g, yield 75%, HPLC: 99.7%, 99.4% ee.
With bis(acetylacetonate)oxovanadium; C27H39NO2Si; dihydrogen peroxide; In acetone; at -5 - 0℃;
After reacting (1R,2S)-prolinol trisilyl ether with 3,5-dimethylsalicaldehyde in an equivalent amount, ligand L2 was obtained (specific process reference: Org. Synth. 2005, 82, 157). The ligand L2 (5.0 mmol) and VO(acac)2 (1.27 g, 4.8 mmol) were added to acetone and stirred for 1 hour. After the color of the system became dark, the TLC reaction was complete. T-butyl disulfideEthyl ether (169.4 g, 0.95 mol) was dissolved in 190 ml of acetone, and the temperature was controlled at -5C to 0C. 30% hydrogen peroxide (1.02 mol) was slowly added dropwise. The addition was completed in about 20-22 hours, and the raw materials and products were kept warm. When the ratio reaches 90:1, it is considered as the end of the reaction. The temperature is controlled to not exceed 35C. The solvent is distilled off under reduced pressure. 400 mL of diethoxymethane (DEM) is added for layering. The organic layer is washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solution is tested for (S)-tert-butyl sulfoxide. Acetyl tert-butyl thioester external standard yield 92% (169.8g, 0.87mol), 96.5% ee;
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