912480-89-8Relevant academic research and scientific papers
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
Jia, Xue-Shun,Wang, Xian-Liang,Xiao, Jun-Zhao,Yin, Liang,Yin, Xing-Hao
supporting information, p. 1916 - 1922 (2021/06/07)
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.
Mechanistic insight into copper-catalysed allylic substitutions with bis(triorganosilyl) zincs. Enantiospecific preparation of α-chiral silanes
Schmidtmann, Eric S.,Oestreich, Martin
, p. 3643 - 3645 (2008/09/20)
Isotopic desymmetrisation, as well as (stereo)chemical correlation, has illuminated significant aspects of the σ-π-σ mechanism of copper-catalysed allylic substitution reactions: an enantiospecific and regioselective access to α-chiral silanes is presente
