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Synfacts 2008(2): 0187-0187  
DOI: 10.1055/s-2007-992481
Metal-Mediated Synthesis
© Georg Thieme Verlag Stuttgart · New York

Highly Stereoselective Catalytic Carbocupration of Alkynoates

Contributor(s): Paul Knochel, Andrei Gavryushin
A. J. Mueller, M. P. Jennings*
The University of Alabama, Tuscaloosa, USA
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Publication History

Publication Date:
23 January 2008 (online)

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Significance

While stoichiometric carbocupration of alkynes was first reported by E. J. Corey about 40 years ago, this publication describes the first both diastereoselective and catalytic method for the addition of Grignard reagents to alkyno­ates. By choosing the additive (TMSCl or TMSOTf) and the proton source (NH4Cl or TFA), the reaction can be switched to the formation of Z- or E-products with high stereoselectivity. Addition of an electrophile allows the preparation of stereodefined trisubstituted acrylates.