Controllable Synthesis of Stereoregular Polyestersby Organocatalytic Alternating Copolymerizations of Cyclohexene Oxideand Norbornene Anhydrides.

A facilestrategy has been demonstrated for the selective synthesisof highly stereoregular polyesters with cis-2,3-(exo,exo) or trans-2,3-(exo,endo) repeating units by the organocatalystsmediated alternating copolymerization of cyclohexene oxide and norborneneanhydride (NA) stereoisomers. The geometrical structure of polyestercan be tuned simply by modulating the type of NA isomers (endo- or exo-NA), monomer feed ratio, andreaction temperature. The cis- (>99%) and trans-polyesters (>99%) exhibit high glass transitiontemperatureup to 129.8 and 115.9 °C, respectively. The resulting polyestersprovide a versatile platform to incorporate various functional groupsthrough the robust thiol–ene reaction of the pendant norbornenylgroups. [ABSTRACT FROM AUTHOR]