Cooperation of Cis Vicinal Acceptors for Donor–Acceptor Cyclopropane Activation: TfOH-Promoted Ring-Opening/Aryl Shift Rearrangement to 3- and 5‑Ylidenebutenolides
journal contributionposted on 2021-01-05, 12:37 authored by Jiru Shao, Qinyuan Luo, Hongyan Bi, Sunewang R. Wang
A convenient route to 3- and 5-ylidenebutenolides from readily available cis-2-acylcyclopropane-1-carboxylates is described. Upon exposure to TfOH, synergistic activation of the vicinal acceptors in cis-2-acylcyclopropane-1-carboxylates generates highly strained bicyclic oxocarbenium ion intermediates, which undergo the ring-opening/aryl shift/deprotonation cascade process to form the 3- or 5-ylidenebutenolides depending on the acyl group. On the other hand, the corresponding trans isomers, from which it is difficult to form such oxocarbenium ions, are inactive under the same conditions.