With independent reports by Bertrand and Arduengo in the late 1980's demonstrating that a divalent carbon moiety can be stable came a renaissance in their use as ligands and catalysts for organic transformations. Since 2000, we have been engaged in the development of chiral nucleophilic carbenes for aldehyde umpolung.  A triazolium precursor can be rapidly and modularly assembled which, upon treatment with a variety of bases, leads to the N-heterocyclic carbene.  These moieties render aldehydes nucleophilic (via the Breslow intermediate) and convert reducible aldehydes into a variety of acid derivatives. In cases where there is the prospect of asymmetric catalysis, tuning of the catalyst framework as well as reaction conditions often leads to high enantioselectivities.  This lecture will outline the historical development of this family of catalysts, insight into their mechanism of action and source of selectivities as well as prospects for the future.

Award Address  (Arthur C. Cope Mid Career Scholars Award sponsored by the Arthur C. Cope Fund). Chiral nucleophilic carbenes for use in organic synthesis: From acyl anion to internal redox catalysis and beyond

248th National Meeting (2014)

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