Enantiopure metal-complex catalyzed asymmetric alternating copolymerization of CO(2) and meso-epoxides is a powerful synthetic strategy for preparing optically active polycarbonates with main-chain chirality. The previous studies regarding chiral zinc catalysts provided amorphous polycarbonates with moderate enantioselectivity, and thus, developing highly stereoregular catalysts for this enantioselective polymerization is highly desirable. Herein, we report the synthesis of highly isotactic poly(cyclohexene carbonate)s from meso-cyclohexene oxide using dissymmetrical enantiopure salenCo(III) complexes in conjunction with bis(triphenylphosphine)iminium chloride (PPNCl) as catalyst. The presence of a chiral induction agent such as (S)-propylene oxide or (S)-2-methyltetrahydrofuran significantly improved the enantioselectivity regarding (S,S)-salenCo(III) catalyst systems. Up to 98:2 of RR:SS was observed in the resultant polycarbonates obtained from the catalyst system based on (S,S)-salenCo(III) complex 4d bearing an adamantyl group on the phenolate ortho position, in the presence of (S)-2-methyltetrahydrofuran. Primary ONIOM (DFT:UFF) calculations, which were performed to investigate the effect of the competitive coordination of (S)-induction agent versus cyclohexene oxide to Co(III) center on enantioselectivity, suggest that the (S)-C-O bond in cyclohexene oxide is more favorable for cleavage, due to the interaction between oxygen atom of (S)-induction agent and (S)-C-H of the coordinated cyclohexene oxide. The highly isotactic poly(cyclohexene carbonate) is a typical semicrystalline polymer, possessing a melting point of 216 °C and a decomposition temperature of 310 °C.

Chiral chromium complexes of tetradentate N,N′‐disubstituted bis(aminophenoxide) (designated as Salan, a saturated version of Schiff‐base Salen ligand) in conjunction with an ionic quaternary ammonium salt can efficiently catalyze the copolymerization of CO2 with racemic propylene oxide (rac‐PO) at mild conditions to selectively afford completely alternating poly(propylene carbonate) (PPC) with ∼ 95% head‐to‐tail linkages and moderate enantioselectivity. These new catalyst systems predominantly exceed the previously much‐studied SalenCr(III) systems in catalytic activity, polymer enantioselectivity, and stereochemistry control. The chiral diamine backbone, sterically hindered substitute groups on the aromatic rings, and the presence of sp3‐hydridized amino donors and its N,N′‐disubstituted groups in chiral SalanCr(III) complexes all play significant roles in controlling polymer stereochemistry and enantioselectivity. Furthermore, a relationship between polycarbonate enantioselectivity and its head‐to‐tail linkages in relation to regioselective ring‐opening of the epoxide was also discussed on the basis of stereochemical studies of PPCs derived from the copolymerization of CO2 with chiral PO at various conditions. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6102–6113, 2008

Producing polyesters with high molecular weight (Mn) through ring‐opening copolymerization (ROCOP) of epoxides with cyclic anhydrides remains a major challenge. Herein, we communicate a metal‐free, highly active, and high thermoresistance system for the ROCOP of epoxides with cyclic anhydrides to prepare polyesters (13 examples). The organoboron catalysts can endure a reaction temperature as high as 180 °C for the ROCOP of cyclohexane oxide (CHO) with phthalic anhydride (PA) without the observation of any side reactions. The average Mn of the produced poly(CHO‐alt‐PA) climbed to 94.5 kDa with low polydispersity (Ð=1.19). Furthermore, an unprecedented turnover number of 9900, equivalent to an efficiency of 7.4 kg of polyester/g of catalyst, was achieved at a feed ratio of CHO/PA/catalyst=20000:10000:1 at 150 °C. Kinetic studies, crystal structure analysis, 11B NMR spectra, and DFT calculations provided mechanistic justification for the effectiveness of the catalyst system.