Tandem Chemoselective Suzuki-Miyaura Cross-Coupling Enabled by Nucleophile Speciation Control

Control of boronic acid speciation is presented as a strategy to achieve nucleophile chemoselectivity in the Suzuki–Miyaura reaction. Combined with simultaneous control of oxidative addition and transmetalation, this enables chemoselective formation of two CC bonds in a single operation, providing a method for the rapid preparation of highly functionalized carbogenic frameworks. Breaking the limit: Chemoselective Suzuki–Miyaura cross‐coupling has previously been limited to single CC bond formation due to a lack of nucleophile selectivity. Manipulation of boron speciation enables complete chemoselective control of the Suzuki–Miyaura reaction, allowing harmonized sequential cross‐coupling in a single operation.