- 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
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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.
- Jia, Xue-Shun,Wang, Xian-Liang,Xiao, Jun-Zhao,Yin, Liang,Yin, Xing-Hao
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supporting information
p. 1916 - 1922
(2021/06/07)
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- Mechanistic insight into copper-catalysed allylic substitutions with bis(triorganosilyl) zincs. Enantiospecific preparation of α-chiral silanes
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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
- Schmidtmann, Eric S.,Oestreich, Martin
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p. 3643 - 3645
(2008/09/20)
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