Ketone displacement and migration enabled by trifunctionalization of vinyl triflates.

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.