Organocatalyzed ROP of a Glucopyranoside Derived Five-Membered Cyclic Carbonate

Abstract

Saccharides, based on their wide bioavailability, high chemical functionality and stereochemical diversity, are attractive starting materials for the development of new synthetic polymers. Established carbonylation methodologies were used to synthesize a 5-membered cyclic carbonate monomer, 4,6-O-benzylidene-2,3-O-carbonyl-α-d-glucopyranoside (MBGC), in high yield (>95%) from a commercially available d-glucopyranoside derivative. The ability of this monomer to undergo ring-opening polymerization (ROP) with a range of organocatalysts, rather than the previously reported anionic initiators, was investigated. These new conditions were developed to widen the functional group tolerance in the polymerization, and achieve better control over the final properties of the polymers. The most promising of the catalysts examined, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), was used in a kinetic study to confirm the well-controlled nature of the ROP. Optimized conditions were then successfully applied to the synthesis o...