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

Abstract This report employs computational methods at unified levels of theory to systematically and comprehensively examine the respective transmetalation mechanisms underpinning classical palladium‐catalyzed Csp2–Csp2 and Csp2–Csp3 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.