Abstract

Comprehensive SummaryMulti‐substituted cyclohexanes play a crucial role as scaffolds in bioactive compounds. While significant progress has been made in synthesizing substituted cyclohexanes, methods for the stereoselective assembly of 1,3‐disubstituted cyclohexanes remain scarce. This study presents a novel approach involving nickel catalysis to achieve stereoselective carboboration of 1,4‐cyclohexadiene. This innovative process allows for the simultaneous introduction of a boron group and an aryl or an alkyl fragment into the 1,4‐cyclohexadiene framework under mild conditions, with exclusive regioselectivity and excellent cis configuration. The resulting products feature a double carbon bond and the incorporation of the boron group, offering significant potential for subsequent transformations and downstream applications.

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