Synthesis of Chiral Boronated 1,4-cis-Cyclohexenes via Ni-Catalyzed Enantioselective Arylboration

Abstract Six-membered ring scaffolds are widely recognized as prevalent structural motifs, which has consequently piqued the growing interest of the organic chemistry community. In this work, we report an Ni-catalyzed regio-, enantio-, and diastereoselective arylboration of 1,3-cyclohexadienes. This reaction utilizes readily accessible bis(pinacolato)diboron (B2pin2) and aryl iodides, offering a convenient approach to synthetically valuable chiral boronated 1,4-cis-cyclohexenes with excellent regio-, enantio-, and diastereoselectivity. Furthermore, the functionally diverse chiral boronated 1,4-cis-cyclohexene derivatives exhibit high reactivity in a variety of downstream transformations. Preliminary mechanistic studies, corroborated by Density Functional Theory (DFT) calculations, offer insights into the underlying causes of the observed regio- and enantioselectivity.