Silicon-mediated enantioselective synthesis of structurally diverse α-amino acid derivatives

• 作者: Guan-Wu Yin Jian Cao Jun-Han Ma Ke-Fang Yang Li Li Li-Wen Xu Xing-Feng Bai Yu-Li Sun Yu-Ming Cui Zheng Xu
• 来源期刊: 中国科学:化学（英文版）
• 年，卷（期）: 2020,（8）
• 所属期刊栏目: ARTICLES
• 页码范围: 1082-1090
• 页数: 9页
• 语种: 英文

摘要

The catalytic asymmetric synthesis of novel and chiral amino acid derivatives with unconventional chemo-,diastereo-,and enantio-selectivity remains a paramount challenge.Herein we reported a novel protocol for the use of highly enantioselective copper-catalyzed cycloaddition of α,β-unsaturated acylsilanes as a springboard reaction for the facile synthesis of structurally diversified pyrrolidines and complicated α-amino esters by desilylation.The newly developed process could provide a wide range of synthetically useful acylsilane-substituted pyrrolidines (ASiP) in high yields and excellent diastereo-and enantioselectivities with Cu/(R)-XylBINAP complex as the catalyst.And the downstream desilylation transformation enables to expand the potntial applications of 1,3-dipolar cycloaddition in the construction of structurally unique amino acid derivatives,in which an unprecedented and concerted fluoride anion-promoted C-X (X=H,Si,N,C) bond cleavage occurred to the enantioselective construction of aldehyde-substituted pyrrolidines,linear cinnamaldehyde or alkene-substituted amino esters in high ee values.