title: Development of Highly Active and Regioselective Catalysts for the Copolymerization of Epoxides with Cyclic Anhydrides: An Unanticipated Effect of Electronic Variation.
abstract: Recent developments in polyester synthesis have established several systems based on zinc, chromium, cobalt, and aluminum catalysts for the ring-opening alternating copolymerization of epoxides with cyclic anhydrides. However, to date, regioselective processes for this copolymerization have remained relatively unexplored. Herein we report the development of a highly active, regioselective system for the copolymerization of a variety of terminal epoxides and cyclic anhydrides. Unexpectedly, electron withdrawing substituents on the salen framework resulted in a more redox stable Co(III) species and longer catalyst lifetime. Using enantiopure propylene oxide, we synthesized semicrystalline polyesters via the copolymerization of a range of epoxide/anhydride monomer pairs.
authors.affiliation: Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University , Ithaca, New York 14853-1301, United States.
authors.forename: Angela M
authors.initials: AM
authors.lastname: DiCiccio
authors.affiliation: Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University , Ithaca, New York 14853-1301, United States.
authors.forename: Julie M
authors.initials: JM
authors.lastname: Longo
authors.affiliation: Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University , Ithaca, New York 14853-1301, United States.
authors.forename: Gabriel G
authors.initials: GG
authors.lastname: Rodríguez-Calero
authors.affiliation: Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University , Ithaca, New York 14853-1301, United States.
authors.forename: Geoffrey W
authors.initials: GW
authors.lastname: Coates