Esterification of glycerol and solketal by oxidative NHC-catalysis under heterogeneous batch and flow conditions

Abstract

The design and synthesis of a set of supported azolium salt pre-catalysts is presented along with their utilization in the production of monoesters of glycerol and solketal by oxidative N-heterocyclic carbene (NHC)-catalysis through batch and continuous-flow approaches. After a propaedeutic study with soluble NHCs, the heterogeneous analogues (silica and polystyrene supports) were tested in a model monoesterification of glycerol using either the Kharasch oxidant or air (in the presence of electron transfer mediators) as the terminal oxidants. The best performing polystyrene-supported triazolium salt pre-catalyst afforded monoacylglycerols (MAGs) in high yields (up to 95%) and almost complete selectivity (monoester/diester >95 : 5) using air and the green solvent Me-THF. The synthesis of fully bio-based MAGs from furfural, 5-hydroxymethylfurfural (HMF), citronellal, and vanillin is also reported. Continuous-flow experiments have been finally performed by fabricating the corresponding packed-bed microreactor, which could be operated for ca. 120 hours with maintenance of conversion efficiency and selectivity.