Poly(N-heterocyclic-carbene)s and their CO2 Adducts as Recyclable Polymer-Supported Organocatalysts for Benzoin Condensation and Transesterification Reactions

Abstract

The synthesis of poly( N -heterocyclic carbene)s, denoted poly(NHC)s, and of their poly(NHC−CO 2 ) adducts for a use in organocatalysis is described. Poly(NHC)s were readily obtained in a three-step sequence of reactions, involving i) the free-radical polymerization of ionic liquid monomers, that is, 1-vinyl-3-alkylimidazolium-type monomers with bromide (Br − ) as counteranion, followed by ii) anion exchange of Br − for bis(trifluoromethanesulfonyl)imide ( − NTf 2 ), of the poly(1-vinyl-3-alkylimidazolium bromide) precursors, affording poly(1-vinyl-3-alkylimidazolium bis(trifluoromethanesulfonyl)imide) derivatives, and iii) deprotonation of the latter polymeric ionic liquids with a strong base. Carbon dioxide (CO 2 ) was found to reversibly react with poly(NHC)s forming relatively air-stable and thermolabile poly(NHC−CO 2 ) adducts. Both poly(NHC)s and their poly(NHC−CO 2 ) adducts were used as polymer-supported organic catalysts and precatalysts, respectively, in transesterification and benzoin condensation reactions under homogeneous conditions. Both types of polymer-supported NHCs were recycled and used several times, but the manipulation of poly(NHC)s −like their molecular NHC analogues- was more complicated owing to their air and moisture sensitivity. In this regard, zwitterionic poly(NHC−CO 2 ) adducts like their molecular NHC−CO 2 analogues could be easier manipulated than their bare poly(NHC) counterparts, providing good to excellent yields even after several organocatalytic cycles, in particular toward the transesterification reaction.