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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
Author(s) -
Wang XianLiang,
Yin XingHao,
Xiao JunZhao,
Jia XueShun,
Yin Liang
Publication year - 2021
Publication title -
chinese journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 1001-604X
DOI - 10.1002/cjoc.202100101
Subject(s) - chemistry , conjugate , silylation , enantioselective synthesis , catalysis , aldehyde , copper , substrate (aquarium) , ligand (biochemistry) , combinatorial chemistry , stereochemistry , organic chemistry , receptor , biochemistry , mathematical analysis , oceanography , mathematics , geology
Main observation and conclusion A general synthesis of chiral 1,3‐disubstituted allylsilanes is established through copper(I)‐catalyzed asymmetric 1,4‐conjugate silylation 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 olefination 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 allylsilanes 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.