Organocatalytic Trapping of Elusive Carbon Dioxide based Heterocycles through a Kinetically Controlled Cascade Process

A conceptually novel approach is described for the synthesis of larger-ring cyclic carbonates derived from carbon dioxide. The approach utilizes homoallylic precursors that are converted into five-membered cyclic carbonates having a beta-positioned alcohol group in one of the ring substituents. The activation of the pendent alcohol group through an N-heterocyclic base allows for equilibration towards a thermodynamically disfavored six-membered carbonate analogue that can be conveniently trapped by an acylation agent. Various control experiments and computational analysis of this manifold are in line with a process that is primarily dictated by a kinetically controlled acylation step. This cascade process delivers an ample diversity of novel six-membered cyclic carbonates in excellent yields and chemoselectivities under remarkably mild reaction conditions. This newly developed protocol helps to expand the repertoire of CO2-based heterocycles that are otherwise difficult to generate by conventional approaches.