Revolutionary reactivity of vinyl cyclopropane: a rhodium-catalyzed enantioconvergent and chemodivergent rearrangement

Vinyl cyclopropanes (VCPs) serve as important three- and five-carbon synthons in organic synthesis; however, functionalization of their two inherently inactive sites remains a significant challenge. To address this, we designed a Rh-catalyzed ring-opening/β-F elimination of vinyl gem-difluorocyclopropanes (VCPdFs) to generate vinylic allyl rhodium intermediates, thereby unlocking novel reactivity of VCP derivatives. In this work, we report a rhodium-catalyzed enantioconvergent rearrangement of racemic VCPdFs that efficiently produces diverse chiral cyclopentenes in chemdivergent manner, including cyclopentenones and gem-difluorocyclopentenes that are challenging to access via conventional methods. This protocol demonstrates excellent chemoselectivity and enantioselectivity, delivering both products in high yields with excellent ee values. The rationalized mechanistic discussion elucidates the reaction pathways and selectivity, all of which are well-supported by experimental evidence. In addition, several chiral cyclopentenones demonstrate therapeutic potential against bladder cancer.