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立构规整端基官能化聚(苯乙炔)的合成:通过末端偶联在铑催化的苯乙炔活性聚合中实现聚(苯乙炔)的末端链端功能化

Synthesis of Stereoregular Telechelic Poly(phenylacetylene)s: Facile Terminal Chain-End Functionalization of Poly(phenylacetylene)s by Terminative Coupling with Acrylates and Acrylamides in Rhodium-Catalyzed Living Polymerization of Phenylacetylenes.

机构信息

Graduate School of Frontier Science Initiative, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan.

Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan.

出版信息

J Am Chem Soc. 2021 Mar 10;143(9):3604-3612. doi: 10.1021/jacs.1c00150. Epub 2021 Feb 18.

Abstract

Various α,β-unsaturated carbonyl compounds, such as acrylates and acrylamides, were quantitatively introduced to the terminal chain end of poly(phenylacetylene)s by C-C bond formation with terminal organorhodium(I) species formed in the living polymerization of phenylacetylenes with a rhodium-based multicomponent catalytic system that we have recently developed, when these carbonyl compounds were used as terminating reagents. This enables the facile and versatile synthesis of stereoregular telechelic poly(phenylacetylene)s with various functional groups at both the initial and terminal chain ends because the components of aryl boronic acid derivatives used as initiators in our multicomponent catalytic system are quantitatively introduced to the initiating end of the resulting polymer.

摘要

各种α,β-不饱和羰基化合物,如丙烯酸酯和丙烯酰胺,可以通过与我们最近开发的基于铑的多组分催化体系中形成的末端有机铑(I)物种的 C-C 键形成定量地引入到聚(苯乙炔)的末端链末端,当这些羰基化合物用作封端试剂时。这使得具有各种官能团的立体规整末端聚(苯乙炔)的简便和通用的合成成为可能,因为在我们的多组分催化体系中用作引发剂的芳基硼酸衍生物的组分定量地引入到所得聚合物的引发端。

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