Stereodivergent Silylzincation of α‑Heteroatom-Substituted Alkynes

Zinc reagents (Me2PhSi)2Zn and [(Me3Si)3Si]2Zn undergo highly regio- and stereoselective addition across the carbon–carbon triple bond of nitrogen-, sulfur-, oxygen-, and phosphorus-substituted terminal alkynes in the absence of copper or any other catalyst. Both reagents yield exclusively β-isomers...

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Bibliographic Details
Published in:Organic letters 2016-05, Vol.18 (9), p.2054-2057
Main Authors: Fopp, Carolin, Romain, Elise, Isaac, Kevin, Chemla, Fabrice, Ferreira, Franck, Jackowski, Olivier, Oestreich, Martin, Perez-Luna, Alejandro
Format: Article
Language:English
Subjects:
Chemical Sciences
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Summary:Zinc reagents (Me2PhSi)2Zn and [(Me3Si)3Si]2Zn undergo highly regio- and stereoselective addition across the carbon–carbon triple bond of nitrogen-, sulfur-, oxygen-, and phosphorus-substituted terminal alkynes in the absence of copper or any other catalyst. Both reagents yield exclusively β-isomers, and the stereoselectivity is determined by the silyl group: Me2PhSi for cis or (Me3Si)3Si for trans. These stereodivergent silylzincation protocols offer an efficient access to heteroatom-substituted vinylsilanes with either double bond geometry, including trisubstituted vinylsilanes by one-pot electrophilic substitution of the intermediate C­(sp2)–Zn bond by copper­(I)-mediated carbon–carbon bond formation.
ISSN:1523-7060
1523-7052
DOI:10.1021/acs.orglett.6b00680