Asymmetric Synthesis of Chiral 1,3-Disubstituted Allylsilanes via Copper(Ⅰ)-Catalyzed 1,4-Conjugate Silylation of α,β-Unsaturated Sulfones and Subsequent Julia-Kocienski Olefination

• 作者: Xian-Liang Wang Xing-Hao Yin Jun-Zhao Xiao Xue-Shun Jia Liang Yin
• 来源期刊: 中国化学（英文版）
• 年，卷（期）: 2021,（7）
• 所属期刊栏目: Concise Reports
• 页码范围: 1916-1922
• 页数: 7页
• 语种: 英文
• DOI: 10.1002/cjoc.202100101

摘要

Main observation and conclusion A general synthesis of chiral 1,3-disubstituted allylsilanes is established through copper(Ⅰ)-catalyzed asymmetric 1,4-conjugate silyla-tion of α,β-unsaturated sulfones and subsequent Julia-Kocienski olefination.By modification of McQuade's NHC ligand,the catalytic asymmetric conjugate silylation with a broad substrate scope is achieved in high enantioselectivity.The following Julia-Kocienski ole-fination proceeds smoothly at room temperature to deliver an array of chiral allylsilanes in moderate yields.More interestingly,a one-pot asymmetric synthesis with high synthetic efficiency is successfully realized.Utility of the prepared chiral 1,3-disubsituted al-lylsilanes is demonstrated in the asymmetric allylation of both aldehyde and aldimine.Finally,an interesting "match and mismatch"phenomenon is observed in the asymmetric allylation of chiral aldehydes.