Ligand-Controlled Regiodivergent Copper-Catalyzed Alkylboration of Alkenes

A novel copper‐catalyzed regiodivergent alkylboration of alkenes with bis(pinacolato)diboron and alkyl halides has been developed. The regioselectivity of the alkylboration was controlled by subtle differences in the ligand structure. The reaction thus enables the practical, regiodivergent synthesis of two different alkyl boronic esters with complex structures from a single alkene. One way or another: The copper‐catalyzed regiodivergent alkylboration of alkenes with bis(pinacolato)diboron and alkyl halides is described. The regioselectivity of the carboboration can be controlled by fine‐tuning the ligand structure.