Abstract Functional group displacement and migration represent powerful, yet underexplored strategies in synthetic chemistry, offering unique opportunities for molecular diversification and drug discovery. Here, we report a nickel-catalyzed deoxygenative trifunctionalization of vinyl triflates, which enables the efficient synthesis of structurally diverse, boron-containing polysubstituted cyclohexanes featuring quaternary carbon centers. This reaction is a key step enabling aryl displacement of a ketone group and its migration to an adjacent carbon center. Notably, the transformation exhibits broad substrate scope and exceptional, programmable diastereoselectivity in arylative ketone migration. Moreover, this transformation enables efficient α -arylation of unsymmetrical ketones with excellent regio- and diastereoselective control—an outcome that remains challenging to achieve using existing methods. Furthermore, this strategy is particularly well-suited for the late-stage functionalization of structurally complex bioactive molecules, facilitating the rapid generation of analogs.
Wang et al. (Fri,) studied this question.