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Organocatalytic Trapping of Elusive Carbon Dioxide Based Heterocycles by a Kinetically Controlled Cascade Process
Author(s) -
Qiao Chang,
VillarYanez Alba,
Sprachmann Josefine,
Limburg Bart,
Bo Carles,
Kleij Arjan W.
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202007350
Subject(s) - chemistry , alcohol , acylation , trapping , carbon dioxide , base (topology) , ring (chemistry) , carbonate , cascade , combinatorial chemistry , organic chemistry , catalysis , ecology , mathematical analysis , mathematics , chromatography , biology
Abstract A conceptually novel approach is described for the synthesis of six‐membered cyclic carbonates derived from carbon dioxide. The approach utilizes homoallylic precursors that are converted into five‐membered cyclic carbonates having a β‐positioned alcohol group in one of the ring substituents. The activation of the pendent alcohol group through an N‐heterocyclic base allows equilibration towards a thermodynamically disfavored six‐membered carbonate analogue that can be trapped by an acylating 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 six‐membered cyclic carbonates in excellent yields and chemoselectivities under mild reaction conditions.