The Transmetalation Process in Suzuki–Miyaura Reactions: Calculations Indicate Lower Barrier via Boronate Intermediate

Abstract Recent experimental reports have called into question the validity of the boronate mechanism (through a RB(OH) 3 − intermediate) for the transmetalation step in the Suzuki–Miyaura cross‐coupling, favoring instead the palladium hydroxo pathway (through an [L n Pd(R′)(OH)] intermediate). Herein we report DFT calculations with the M06 functional performed on realistic model systems, including a combination of explicit solvent molecules along with a continuum method. These computational results support the boronate mechanism. The mechanistic proposal is shown to be compatible with the available experimental evidence.