Alkyne Hydroarylations with Chelating Dicarbene Palladium(II) Complex Catalysts: Improved and Unexpected Reactivity Patterns Disclosed Upon Additive Screening

Graphical Abstract

By choosing the right additives, the title compounds were found to efficiently catalyse the hydroarylation of alkynes at roomtemperature and with controllable selectivity

Abstract

Palladium(II) complexes with a ligand set made from a chelating N-heterocyclic dicarbene ligand and two weakly coordinating anions (generally introduced in situ upon addition of 2 equiv. of a suitable silver salt) were found to be very active and selective catalysts for the room-temperature hydroarylation of alkynes at low catalyst loading (0.1 mol-%). Moreover, the screening of various strong acids as reaction promoters revealed that both the strength of the acid and the coordinating ability of its conjugated base influence the catalytic performance. Most remarkably, the use of HBF₄ together with a dicarbene Pd complex catalyst provides a dramatic change in the selectivity of the reaction, with the prevalent formation of a product stemming from the insertion of two molecules of alkyne into the aromatic C–H bond. The results presented herein highlight the fact that the dicarbene ligand, apart from stabilising the catalyst, is also able to enhance catalytic activity and, most notably, to steer the reaction selectivity towards novel products. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)