Stereochemistry-Tunable Isocyanide-Based Polymerization

摘要

Regulation of stereochemistry is one of the most important research focuses in synthetic polymer chemistry; however, this area should be further developed. In this work, a new polymerization of diisocyanoacetates and disulfonimines with tunable stereochemistry was developed. Diisocyanoacetates and disulfonimines could easily undergo polycycloaddition in the presence of CuCl/PPh3, and polyimidazolines with high weight-average molecular weights (M-w, up to 43 900) were produced in excellent yields (up to 99%). Moreover, the stereochemistry of the polymerization and the stereoregularity of the resultant polymers can be fine-tuned by triethylamine (TEA). In addition, TEA could also significantly promote the polymerization, from which polymers with much higher molecular weights (M-w up to 155 400) could be obtained in higher yields. This work not only promotes the development of the isocyanide chemistry and enriches the family of polymerizations based on triple-bond building blocks but also provides an opportunity to study the structure-property relationship of the polyimidazolines.

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