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Enantiomer-selective Living Polymerization of rac-Phenyl Isocyanide Using Chiral Palladium Catalyst

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Abstract

We report the polymerization of phenyl isocyanides with the chiral palladium(II) initiating system. The resulting polymers with optically active properties were obtained by polymerization of the racemic isocyanide monomer (rac-1), and enantiomerically unbalanced polymerization of the monomer was found, providing substantial evidence for the enantiomer-selective polymerization of rac-1 mediated through chiral catalyst. A comparison between the enantiomerically pure monomers, 4-isocyanobenzoyl-L-alanine decyl ester (1s) and 4-isocyanobenzoyl-D-alanine decyl ester (1r), revealed a drastic discrepancy in the reactivity ratio of their homopolymerizations. It turned out that the monomer reactivity ratio of 1s was higher than that of 1r with chiral ligands. The results clearly demonstrated the inclination for incorporation of the 1s enantiomer during the polymerization process and thus resulted in the enantiomer-selective polymerization in this system. The effects of the catalyst chirality on the optically active properties of polymerization were investigated, and it was concluded that the formation of higher-ordered conformation with a handed helicity might be attributed to the chiral induction of chiral palladium(II) catalyst. Moreover, the polymers obtained through the enantiomer-selective polymerization of the enantiomerically pure monomer were with a significant improvement of the optical activity if the chirality of the monomer and the catalyst matched with each other.

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Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (Nos. 51673057, 21622402, and 21574036). N. Liu thanks Anhui Provincial Natural Science Foundation (No. 1608085MB41).

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Authors and Affiliations

  1. Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, Hefei University of Technology and Anhui Key Laboratory of Advanced Catalytic Materials and Reaction Engineering, Hefei, 230009, China

    Jian Huang, Ling Shen, Hui Zou & Na Liu

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  1. Jian Huang
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  2. Ling Shen
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  4. Na Liu
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Correspondence to Na Liu.

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Huang, J., Shen, L., Zou, H. et al. Enantiomer-selective Living Polymerization of rac-Phenyl Isocyanide Using Chiral Palladium Catalyst. Chin J Polym Sci 36, 799–804 (2018). https://doi.org/10.1007/s10118-018-2136-5

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