(S)-tert-Butanethiosulfinate synthesis

Yield: 92%

Reaction Conditions:

with bis(acetylacetonate)oxovanadium;C₂₇H₃₉NO₂Si;dihydrogen peroxide in acetone at -5 - 0;

Steps:

2.2 Example 2
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. 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 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 92% (169.8g, 0.87mol), 96.5% ee;

References:

Shanghai Hanhong Technology Co., Ltd.;Ma Shizhong;Tan Zaipei;Zhang Baohua;Zha Liangxing;Du Xianglong CN106478471, 2017, A Location in patent:Paragraph 0018; 0019