Intriguing Electrophilic Reactivity of Donor–Acceptor Cyclopropanes: Experimental and Theoretical Studies

Abstract

A new reactivity of donor–acceptor cyclopropanes (DACs) has been highlighted and, for the first time, we report that they could formally behave as nucleophiles and be functionalized at their C3 position. The donor–acceptor cyclopropane acts as a formal nucleophilic synthetic equivalent of a 1,2‐zwitterion and could be described as an umpolung synthon. A highly substituted lactone is reached, and even more impressive is the formation of four stereogenic centers with complete control of their relative configuration. Both experimental and computational studies were performed to provide an overall picture of the mechanism.