Acyclic diaminocarbene (ADC) ligands have potential advantages over the more widely studied N-heterocyclic carbenes in asymmetric catalysis, because their wide N-C-N angles can place chiral substituents closer to the reactive metal. In pursuit of useful, gold-catalyzed enantioselective transformations, we have prepared a series of gold(I) complexes of chiral ADC ligands. Treatment of gold(I) complexes of variously substituted, axially chiral binaphthyl isocyanides with achiral or chiral amines afforded the new ADC ligands in good to high yields. X-ray crystallographic and NMR studies identified different secondary interactions of the gold center with aryl rings attached to the binaphthyl 2�-position of the ADC ligand or with one of the naphthyl rings, depending on the substitution patterns of the ADC nitrogens and the binaphthyl moiety. The presence of these interactions correlated with highly enantioselective catalysis of alkynylbenzaldehyde cyclization reactions.

Chiral gold-acyclic diaminocarbene complexes displaying metal-ligand secondary interactions

246th National Meeting (2013)

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