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Synthesis 2008(8): 1306-1315
DOI: 10.1055/s-2008-1072516
DOI: 10.1055/s-2008-1072516
FEATUREARTICLE
© Georg Thieme Verlag Stuttgart · New York
Protonation of Homoenolate Equivalents Generated by N-Heterocyclic Carbenes
Further Information
Received
22 February 2008
Publication Date:
18 March 2008 (online)
Publication History
Publication Date:
18 March 2008 (online)
Abstract
Homoenolate equivalents are generated by Lewis basic N-heterocyclic carbene catalysts and then protonated to generate efficiently saturated esters from unsaturated aldehydes. This reactivity is extended to the generation of β-acylvinyl anions from alkynyl aldehydes. The asymmetric protonation of a homoenolate equivalent generated from a β,β-disubstituted aldehyde can be accomplished with a chiral N-heterocyclic carbene.
Key words
carbenes - umpolung - protonations - asymmetric catalysis - esters
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References
Our preliminary studies of generating homoenolates using N-heterocyclic carbenes and the protonation of these unusual intermediates was first described in a lecture by K.A.S. at the 2004 Natural Products Gordon Research Conference (Tilton, NH) on Thursday, July 29, 2004.