Vinylogous Fluorine Stabilizing Effect Enables Rational Design of a Novel Donor-Acceptor Cyclopropane and Its Applications in [3+2] Cycloaddition Reaction and Ring-Opening Polymerization

Abstract

Discovery of unprecedented donor-acceptor patterns can essentially enrich the chemistry of donor-acceptor cyclopropanes. We herein introduce a concept of vinylogous fluorine stabilizing effect, which guides rational design of a novel donor-acceptor cyclopropane employing gem-difluorovinyl group as the electron donor, namely dFVCP. Application of such dFVCPs in a [3+2] cycloaddition with aldehydes and a controlled ring-opening polymerization by a Mg(OTf) ₂/DIPEA/C(sp ³)-H initiator system have been demonstrated, providing direct access to fluorine-containing tetrahydrofurans and all-carbon main-chain polymers.

Keywords

Donor-acceptor cyclopropane / gem-Difluorovinyl group / Vinylogous fluorine stabilizing effect / [3+2] cycloaddition / Ring-opening polymerization / Strained molecules / Monomers / Ionic polymerization

RIGHTS & PERMISSIONS

2024 SIOC, CAS, Shanghai, & WILEY-VCH GmbH