Silver catalyzed proto- and sila-Nakamura-type α-vinylation of silyl enol ethers with dichloroacetylene. Divergent formation of stereochemically pure tri- and tetrasubstituted olefins

[Display omitted] •Silver catalyzed activation of dichloroacetylene towards addition.•Highly trans selective addition of enol ether across dichloroacetylene.•Silyl versus proton transfer controlled via solvent.•Highly functionalized tri- and tetrasubstituted alkenes selectively obtained.•Unusual CH...

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Bibliographic Details
Published in:Tetrahedron letters 2020-01, Vol.61 (2), p.151370, Article 151370
Main Authors: Li, Lun, Wasik, Kimberly A., Frost, Brian J., Geary, Laina M.
Format: Article
Language:English
Subjects:
Nakamura-type
Silver catalyzed
Stereoselective
Vinylation
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Summary:[Display omitted] •Silver catalyzed activation of dichloroacetylene towards addition.•Highly trans selective addition of enol ether across dichloroacetylene.•Silyl versus proton transfer controlled via solvent.•Highly functionalized tri- and tetrasubstituted alkenes selectively obtained.•Unusual CH silylation observed in select cases. The silver-catalyzed reaction of silyl enol ethers with dichloroacetylene (DCA) is described. When DCA was used as a solution in diethyl ether, we found that the silyl group was transferred to the vinyl group, resulting in stereochemically pure tetrasubstituted olefins. However, when DCA was used as a solution in the more polar acetonitrile, protonation was the major pathway, and trisubstituted olefins were the dominant products.
ISSN:0040-4039
DOI:10.1016/j.tetlet.2019.151370