- 作者: 周善行 ; 趙懋勳
- 作者服務機構: 輔仁大學化學系
- 中文摘要: Treatment of 3-phenylthio-2-sulfolene with an equimolar proportion of butyllithium at -78.degree.C in THF followed by addition of an electrophile gave the 2- substituted 3-phenylthio-2-sulfolenes (2). The deprotonation was found to proceed only at the vinylic C-2 position. Some of the 2-sulfolenes (2) underwent desulfonylation upon heating with base. Of particular interest was the conversion of 3-phenylthio-2- trimethylsilyl-2-sulfolene (2h) to its 3-sulfolene isomer(6) by sequential addition of butyllithium and salicylic acid at low temperatures. The 3-sulfolene (6) was desulfonylated by Kugelrohr distillation at 150.degree.C under vacuum to give (Z)-2-phenylthio-1-trimethylsilyl-1,3- butadiene (8). The regiochemistry of the Diels Alder reaction of this highly reactive diene 8 was found to be controlled by the phenylthio group, and the stereochemistry is endo addition. Diene 8 was oxidized to its sulfone derivative 12 which also underwent a stereospecific Diels- Alder reaction.
- 英文摘要: --
- 中文關鍵字: Deprotonation; Diels-Alder Reaction; Synthesis; Stereochemistry; Sulfolene
- 英文關鍵字: 去質子化;Diels-Alder反應;合成;立體化學;磺烯