Coordinating heterocycles and amines are ubiquitous motifs in many pharmaceuticals, natural products, and materials but frequently cause compatibility issues for transition metal catalysis due to poisoning. We report a general strategy for palladium-catalyzed, non-directed C–H functionalizations that tolerates 1°, 2°, or 3° amines as well as a range of N-heteroaromatics, such as pyridines and imidazoles. The simple thioether ligand [(p-FC6H4)S(CH2)4SO3−] was effective at generating a catalyst with high activity even in the presence of stoichiometric Brønsted acid as a masking reagent. Directed C–H functionalization by amines or coordinating heterocycles is also deactivated by this approach to access complementary site selectivity. A robustness screening assay under these conditions found, counterintuitively, higher functional group tolerance actually correlates with more Lewis basic additives, which contrasts typical compatibility trends.

General solution to amine and heterocycle poisoning during C–H alkenylation, arylation, and carbonylation using thioether-palladium catalysis

2019 Spring National Meeting

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