Rhodium Catalyzed Regioselective C−H Allylation of Simple Arenes via C−C Bond Activation of <italic>Gem</italic>‐difluorinated Cyclopropanes.

Herein, we report a rhodium catalyzed directing‐group free regioselective C−H allylation of simple arenes. Readily available <italic>gem</italic>‐difluorinated cyclopropanes can be employed as highly reactive allyl surrogates via a sequence of C−C and C−F bond activation, providing allyl arene derivatives in good yields with high regioselectivity under mild conditions. The robust methodology enables facile late‐stage functionalization of complex bioactive molecules. The high efficiency of this reaction is also demonstrated by the high turnover number (TON, up to 1700) of the rhodium catalyst on gram‐scale experiments. Preliminary success on kinetic resolution of this transformation is achieved, providing a promising access to enantio‐enriched <italic>gem</italic>‐difluorinated cyclopropanes. [ABSTRACT FROM AUTHOR]