Organocatalytic Upgrading of Furfural and 5-Hydroxymethyl Furfural to C(10) and C(12) Furoins with Quantitative Yield and Atom-Efficiency

There is increasing interest in the upgrading of C(5) furfural (FF) and C(6) 5-hydroxymethyl furfural (HMF) into C(10) and C(12) furoins as higher energy-density intermediates for renewable chemicals, materials, and biofuels. This work utilizes the organocatalytic approach, using the in situ generated N,S-heterocyclic carbene catalyst derived from thiazolium ionic liquids (ILs), to achieve highly efficient self-coupling reactions of FF and HMF. Specifically, variations of the thiazolium IL structure have led to the most active and efficient catalyst system of the current series, which is derived from a new thiazolium IL carrying the electron-donating acetate group at the 5-ring position. For FF coupling by this IL (0.1 mol %, 60 °C, 1 h), when combined with Et(3)N, furoin was obtained in >99% yield. A 97% yield of the C(12) furoin was also achieved from the HMF coupling by this catalyst system (10 mol % loading, 120 °C, 3 h). On the other hand, the thiazolium IL bearing the electron-withdrawing group at the 5-ring position is the least active and efficient catalyst. The mechanistic aspects of the coupling reaction by the thiazolium catalyst system have also been examined and a mechanism has been proposed.