Enals under the catalysis of N-heterocyclic carbenes (NHC), generate homoenolate, enolate, and acyl anion equivalents for enantioselective reactions via the activation of �, a, and carbonyl carbons of enals, respectively, as the prenucleophiles. The controlled activation of enal ?-carbon for enantioselective reactions has remained a challenge due to the competing side reactions and being placed relatively remote to the chiral catalyst. Herein we report the first NHC-catalyzed oxidative ?-addition of enals to trifluoromethyl ketones via NHC-bounded vinyl enolate intermediates. High enantioselectivity was achieved via Lewis acid [Sc(OTf)3 or combined Sc(OTf)3/Mg(OTf)2] and NHC cooperative catalysis. Our other efforts in oxidative functionalization of aldehydes will also be discussed.

Oxidative N-heterocyclic carbene catalysis: Remote-activation and cooperative chiral controls for enals

245th National Meeting (2013)

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