Suzuki‐Miyaura Cross‐Couplings: Juxtaposing the Transmetalation of Arylboronic Acids and Alkylboranes

This report employs computational methods at unified levels of theory to systematically and comprehensively examine the respective transmetalation mechanisms underpinning classical palladium-catalyzed C_sp ²-C_sp ² and C_sp ²-C_sp ³ Suzuki-Miyaura cross-couplings. This approach enabled fundamental aspects of these transmetalation pathways to be directly juxtaposed, which allowed for subtle, but important, features underpinning the transmetalation mechanisms of archetypal arylboronic acid and B-alkyl-9-borabicyclo[3.3.1]nonane nucleophiles to be highlighted and placed in a broader context.