Asymmetric Modular Synthesis of Highly Functionalized Medium-Sized Carbocycles and Lactones via Ring-Closing Metathesis of Sulfoximine-Substituted Trienes

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• 作者：Michal Lejkowski ; Hans-Joachim Gais ; Prabal Banerjee ; Cornelia Vermeeren
• 刊名：Journal of the American Chemical Society
• 出版年：2006
• 出版时间：December 6, 2006
• 年：2006
• 卷：128
• 期：48
• 页码：15378 - 15379
• 全文大小：84K
• 年卷期：v.128,no.48(December 6, 2006)
• ISSN：1520-5126

文摘

A modular asymmetric synthesis of medium-sized carbocycles and lactones has been developed that affords highly substituted 7-, 9-, and 11-membered rings. The key steps are (1) the highly diastereoselective synthesis of sulfoximine-substituted homoallylic alcohols from allylic sulfoximines and unsaturated as well as saturated aldehydes, (2) an E-stereoselective alkylation and hydroxyalkylation of sulfoximine-substituted alkenyllithium derivatives, (3) the esterification of sulfoximine-substituted homoallylic alcohols, and (4) the ring-closing metathesis reaction of sulfoximine-substituted trienes with the ruthenium catalyst 8. Two examples for the further synthetic elaboration of the sulfoximine-substituted carbocycles are provided. The selective cleavage of the tert-butyldimethylsilyl group of 12 in the presence of the triethylsilyl group afforded the allylic alcohol 18 which was oxidized to enone 19. A cross-coupling reaction of the sulfoximine-substituted carbocycle 9 with LiCuMe₂ furnished the methyl-substituted derivative 20.