Oxidation of Sulfides and silyl Enol Ether by Superoxide and Trimethyl Chloride via Timethylsilylperoxyl Intermediates.

• Main Authors: Yu-Ping Huang, 黃怡萍
• Other Authors: Yao-Jung Chen
• Format: Others
• Language: zh-TW
• Published: 2001
• Online Access: http://ndltd.ncl.edu.tw/handle/35927230383878546902

碩士 === 國立中興大學 === 化學系 === 89 === we reported chemoselective and efficient oxidation of various sulfides, bear keton, olefin, ether, and hydroxyl functionalities, were mediated by trimethylsilyl chloride and potassium superoxide in dry acetonitrile at —15oC to afford the correspoding sulfoxides 60a - 68a in excellent yields (90~98%) together with traceable amount of the sulfones. (Table 4) To continue our studies on the application of silylperoxyl intermediates 69、70、71 generated in situ in the course of the reaction process in a broader scope of organic synthesis, we plan to investigate cyclization reactions of unsaturated enol silyl ether 74 with KO2 and TMSCl in various solvents under milder reaction condition. Based on our previous results, silylperoxyl radical 70 has been found to be a strongly electrophilic oxidizing ability towards sulfides. Unfortunately, the plan were not completed, but we isolated the compounds 80、81、82. Thus, we will focus our attentions on one of the most interesting discoverys (Eq.28) , which silylperoxy intermediates 69、70、71 generated from superoxides and trimethylsilyl chloride can act as potent oxidants.