Ni-catalyzed enantioselective synthesis of β-aminoboronates via spin-center shift and proton transfer

The spin-center shift (SCS) process, involving 1,2-radical migrations, plays a pivotal role in both biological transformations and organic synthesis. While the potential of combining SCS with transition metal-catalyzed enantioselective reductive coupling of electrophiles to construct Csp³-Csp³ bonds at remote positions is highly attractive, this strategy has remained unexplored to date. Here, we report an enantioselective Ni-catalyzed reductive cross-coupling for the synthesis of β-aminoboronates. Our catalytic system operates under mild conditions, achieving excellent enantioselectivity while maintaining broad functional group compatibility. Mechanistic studies, including detailed density functional theory (DFT) calculations, demonstrate the synergistic involvement of both SCS and proton transfer (P.T.) processes in the reaction pathway.