Long-range isomerisation/cyclopropane isomerisation/cycloisomerisation/aromatisation reactions using multifunctional...

Transition-metal-catalyzed chain-walking reactions have emerged as a powerful strategy for remote functionalization of alkenes; however, their integration with C-C bond activation remains largely unexplored. Herein, we report a rhodium-catalyzed reaction that combines long-range alkyl chain-walking with selective cyclopropyl C-C bond cleavage within a single catalytic system. In this transformation, migratory alkene isomerisation across extended carbon frameworks enables distal activation of a cyclopropylmethyl unit, leading to the efficient formation of substituted benzofurans under mild conditions. Unlike conventional chain-walking processes that terminate in remote functionalization, the present system exploits catalyst migration as a prerequisite for subsequent C-C bond activation at a spatially separated site. Mechanistic investigations, including temperature-controlled and time-resolved NMR studies, support a sequential pathway involving alkene chain-walking followed by cyclopropane activation. This work demonstrates a cooperative catalytic strategy that orchestrates spatially separated reaction events and expands the conceptual scope of chain-walking catalysis in organic synthesis.