Aminative Suzuki–Miyaura Coupling: Tackling Alkyl Nucleophiles and Addressing the Viability of the Electrophile‐First Mechanism

Abstract Insertive cross‐coupling reactions provide the option of repurposing widely available coupling partners for the formation of new linkages. By confronting a major limitation of the aminative Suzuki–Miyaura methods we recently reported, we achieve a general method for the Pd‐catalyzed aminative coupling of primary and secondary alkyl boronic esters with aryl (pseudo)halides. Introducing a formal nitrene insertion into this Suzuki–Miyaura reaction diverts the outcome from the traditional C(sp 2 )─C(sp 3 ) products to the C(sp 2 )─NH─C(sp 3 ) analogues ( N ‐aryl anilines). DFT calculations and experimental mechanistic studies indicate that C─N bond formation from the electrophilic aryl component occurs first, providing further evidence for this previously hypothetical pathway. By comparison of several transition state structures, we find that C─N bond formation likely takes place through an unusual dyotropic rearrangement of a LPd(Ar)NHX complex (X = OPOPh 2 ).