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<p>The asymmetric alternating copolymerization of <i>meso</i>-epoxide and cyclic anhydrides provides an efficient access to enantiopure polyesters. Contrary to the extensive investigation of the stereochemistry resulting from epoxide building block, the chirality from anhydride and the configurational match with epoxide remain elusive. Herein, we discover that the bimetallic chromium catalysts have led to an obvious enhancement in terms of reactivity and enantioselectivity for the asymmetric copolymerization of <i>meso</i>-epoxide with various non-symmetric chiral anhydrides. Up to 97% <i>ee</i> was obtained during the asymmetric copolymerization of cyclohexene oxide (CHO) with (<i>R</i>)-methylsuccinic anhydride (<i>R</i>-MSA), and three- or four-carbon chiral centers were simultaneously installed in the aliphatic polyester backbone. In particular, the different combinations of stereochemistry in epoxide and anhydride building blocks considerably affect the thermal properties and crystalline behaviors of the resulting polyesters. This study uncovers an interesting method for regulating polymer crystallinity <i>via</i> matching the chirality of different monomers.</p>

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Installation of Multiple Chiral Centers in Aliphatic Polyesters Backbone Enables Unexpected Crystallinity via Asymmetric Catalytic Copolymerization

  • 期刊论文

  • 发表日期：

    2025年1月25日

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  • Zheng-Fei Liu,
  • Bai-Hao Ren,
  • Yi-Shu Fu,
  • Jun Yang,
  • Yong-Qiang Teng,
  • Ye Liu,
  • Xiao-Bing Lu

摘要

The asymmetric alternating copolymerization of meso-epoxide and cyclic anhydrides provides an efficient access to enantiopure polyesters. Contrary to the extensive investigation of the stereochemistry resulting from epoxide building block, the chirality from anhydride and the configurational match with epoxide remain elusive. Herein, we discover that the bimetallic chromium catalysts have led to an obvious enhancement in terms of reactivity and enantioselectivity for the asymmetric copolymerization of meso-epoxide with various non-symmetric chiral anhydrides. Up to 97% ee was obtained during the asymmetric copolymerization of cyclohexene oxide (CHO) with (R)-methylsuccinic anhydride (R-MSA), and three- or four-carbon chiral centers were simultaneously installed in the aliphatic polyester backbone. In particular, the different combinations of stereochemistry in epoxide and anhydride building blocks considerably affect the thermal properties and crystalline behaviors of the resulting polyesters. This study uncovers an interesting method for regulating polymer crystallinity via matching the chirality of different monomers.