CuCl-Promoted β‑Acylation of Cyclopropanols with Thioesters

CuCl-induced cyclopropyl alcohol ring-opening followed
by β-acylation
with thioester is reported. Cyclopropanols and thioesters with various
substitution patterns were successfully subjected to the reaction,
and a series of 1,4-dicarbonyl compounds were synthesized. The mechanistic
investigation revealed the involvement of Cu(I)-homoenolate, which
reacts with the thioester via oxidative addition. Both experimental
and computational evidence were found. Operational simplicity, high
chemo- and regioselectivity, and good to excellent yields are the
core features of the presented approach.