Preparation of Poly(beta-malic acid) via Direct Carbonylative Polymerization of Benzyl Glycidate

Poly(malic acid) (PMLA) is a water-soluble, biodegradable, biocompatible, and nontoxic polyester in the poly(hydroxyalkanoate) (PHA) family. it features various applications in pharmaceutical field. Here, NaCo(CO)(4) and pyridine derivatives are employed for direct carbonylative polymerization of benzyl glycidate (BG) for poly(beta-malic acid) production. Further investigation on reaction mechanism reveals that this polymerization undergoes a direct chain growth, rather than a sequential process involving beta-lactone intermediate. The low cost and facile preparation of epoxide substrate render this methodology extremely appealing that avoids the rather tedious procedures for beta-malolactonate synthesis required toward ring opening polymerization. This study also represents an alternative strategy over traditional methods for poly(beta-malic acid) production using step growth polycondensation of malic acid.