Despite rapid growth in the use of N-heterocyclic carbene (NHC) and related acyclic diaminocarbene (ADC) ligands in transition metal catalysis, strategies for tuning the steric and electronic parameters of these ligands are still underdeveloped. Metal-templated addition of amines to isocyanides has proven to be a versatile route to catalytically useful, tunable ADC ligands. Readily accessible isocyanide and amine synthons, in combination with electrophilic late transition metals such as palladium and gold, enable rapid access to structurally diverse libraries of new chiral or achiral ADC complexes. These ligands demonstrate some potential advantages over the more widely NHCs in certain reactions due to their unique donor properties and their wide N-C-N angles, which can place bulky and/or chiral substituents closer to the metal. Changes in regio- or enantioselectivity of a variety of palladium- and gold-catalyzed organic transformations have been achieved by systematic variation of the ADC structure.

Micromanaging metal catalysts with structurally tunable acyclic carbene ligands

249th National Meeting (2015)

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