Through a detailed analysis of the physical/structural properties of Pd-NHC complexes, which includes NMR spectroscopy, rate studies, and calculation, a high-performing catalyst has been developed that very effectively cross-couples amines and sulfides to aryl chlorides using mild reaction conditions. In this presentation, the evolution of this catalyst, Pd-PEPPSI-IPent, will be discussed and a wide sampling of examples will be presented demonstrating the general utility and high reactivity of this NHC-derived catalyst. In particular, the role and structure of the base will be evaluated, which in general has been overlooked. This has led to the design and synthesis of a new base specifically for amination that shows excellent kinetics with a variety of NHC- and phosphane-based catalysts when compared with commonly used carbonate bases. Importantly, this base complete high functional group compatibility, unlike potassium or sodium -tert-butoxide, which are also commonly used and have very high reactivity.

Recent advances in metal-catalyzed amination using Pd-NHC complexes: The structure and role of the base

243rd National Meeting (2012)

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