Trans-Selective Radical Silylzincation of Ynamides

The silylzincation of terminal ynamides is achieved through a radical‐chain process involving (Me3Si)3SiH and R2Zn. A potentially competing polar mechanism is excluded on the basis of diagnostic control experiments. The unique feature of this addition across the CC bond is its trans selectivity. On...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2014-10, Vol.53 (42), p.11333-11337
Main Authors: Romain, Elise, Fopp, Carolin, Chemla, Fabrice, Ferreira, Franck, Jackowski, Olivier, Oestreich, Martin, Perez-Luna, Alejandro
Format: Article
Language:English
Subjects:
Bonding
copper
Diagnostic systems
Modular
radical reactions
Radicals
Selectivity
silicon
silylmetalation
Terminals
Transformations
Zinc
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Summary:The silylzincation of terminal ynamides is achieved through a radical‐chain process involving (Me3Si)3SiH and R2Zn. A potentially competing polar mechanism is excluded on the basis of diagnostic control experiments. The unique feature of this addition across the CC bond is its trans selectivity. One‐pot electrophilic substitution of the C sp 2Zn bond by CuI‐mediated CC bond formation and subsequent manipulation of the C sp 2Si bond provides a modular access to Z‐α,β‐disubstituted enamides. A radical­ transformation: Z‐configured α,β‐disubstituted enamides are obtained through a regio‐ and stereoselective silylzincation of terminal ynamides and subsequent sequential functionalization of the resulting C sp 2Zn and C sp 2Si bonds (see scheme). The trans‐selective silylzincation proceeds through a radical process combining organosilyl radical and radical Zn‐atom transfer chemistry.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201407002