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Chemoselective transesterification and polymer synthesis using a zincate complex
Polymer Journal ( IF 2.3 ) Pub Date : 2020-09-18 , DOI: 10.1038/s41428-020-00416-4
Miyuki Oshimura

In this focused review, I present an overview of our recent research on the zincate complex dilithium tetra-tert-butylzincate (TBZL)-catalyzed ring-opening polymerization (ROP) of ε-caprolactone, efficient acylation and transesterification of alcohols with vinyl acetate and carboxylic esters, and polymer synthesis with a high transesterification ability. In the first part of this report, the ROP of ε-caprolactone catalyzed by TBZL in toluene is described. In a subsequent study of the ROP of ε-caprolactone in the presence of 2-hydroxyethyl methacrylate (HEMA), TBZL was found to act not only as an anionic initiator but also as a transesterification catalyst. In the second part of this report, the acylation and transesterification of alcohols with vinyl acetate and carboxylic esters catalyzed by TBZL are summarized. The acylation proceeded quantitatively at 0 °C within 1 h. A wide range of combinations of esters and alcohols were suitable for the transesterification at 0 to −40 °C. In addition, the transesterification proceeded chemoselectively even in the presence of H2O and amines. Next, TBZL-catalyzed polycondensations of diphenyl carbonate (DPC) with diols are discussed. Irreversible polycondensations catalyzed by TBZL occurred to yield aliphatic polycarbonates under atmospheric pressure. In the last part of this report, the transesterifications of poly(phenyl methacrylate) (PPhMA) side chains with alcohols catalyzed by TBZL are described. The transesterification reaction not only with alkyl alcohols but also with fluoroalcohols occurred. By changing the reaction solvent and temperature, the degree of conversion could be controlled. The present system permits the partial, quantitative, or terminal conversion of polymethacrylates. Our recent studies on the zincate complex dilithium tetra-tert-butylzincate-catalyzed transesterification and polymerization are reviewed. In the first part of this report, the ROP of ε-caprolactone catalyzed by TBZL is described. In the second part of this report, the acylation and transesterification of alcohols with vinyl acetate and carboxylic esters catalyzed by TBZL are summarized. Next, TBZL-catalyzed polycondensations of diphenyl carbonate (DPC) with diols are discussed. In the last part of this report, the transesterifications of poly(phenyl methacrylate) (PPhMA) side chains with alcohols catalyzed by TBZL are described.

中文翻译:

使用锌酸盐络合物的化学选择性酯交换和聚合物合成

在这篇重点综述中,我概述了我们最近对锌酸络合物四叔丁基锌酸二锂 (TBZL) 催化的 ε-己内酯开环聚合 (ROP)、醇与乙酸乙烯酯的有效酰化和酯交换以及羧酸酯和具有高酯交换能力的聚合物合成。在本报告的第一部分,描述了 TBZL 在甲苯中催化的 ε-己内酯的 ROP。在随后对 ε-己内酯在甲基丙烯酸 2-羟乙酯 (HEMA) 存在下的 ROP 的研究中,发现 TBZL 不仅充当阴离子引发剂,而且充当酯交换催化剂。在本报告的第二部分,总结了 TBZL 催化醇与乙酸乙烯酯和羧酸酯的酰化和酯交换。酰化在 0°C 下在 1 小时内定量进行。多种酯和醇的组合适用于 0 至 -40 °C 的酯交换。此外,即使在 H2O 和胺存在的情况下,酯交换也能化学选择性地进行。接下来,讨论了 TBZL 催化的碳酸二苯酯 (DPC) 与二醇的缩聚反应。TBZL 催化的不可逆缩聚反应在大气压下产生脂肪族聚碳酸酯。在本报告的最后一部分,描述了聚甲基丙烯酸苯酯 (PPhMA) 侧链与由 TBZL 催化的醇的酯交换。不仅与烷基醇发生酯交换反应,而且与氟代醇发生酯交换反应。通过改变反应溶剂和温度,可以控制转化程度。本系统允许聚甲基丙烯酸酯的部分、定量或末端转化。综述了我们最近对锌酸盐络合物二锂四叔丁基锌酸盐催化的酯交换和聚合的研究。在本报告的第一部分,描述了 TBZL 催化的 ε-己内酯的 ROP。在本报告的第二部分,总结了 TBZL 催化醇与乙酸乙烯酯和羧酸酯的酰化和酯交换。接下来,讨论了 TBZL 催化的碳酸二苯酯 (DPC) 与二醇的缩聚反应。在本报告的最后一部分,描述了聚甲基丙烯酸苯酯 (PPhMA) 侧链与由 TBZL 催化的醇的酯交换。综述了我们最近对锌酸盐络合物二锂四叔丁基锌酸盐催化的酯交换和聚合的研究。在本报告的第一部分中,描述了 TBZL 催化的 ε-己内酯的 ROP。在本报告的第二部分,总结了 TBZL 催化醇与乙酸乙烯酯和羧酸酯的酰化和酯交换。接下来,讨论了 TBZL 催化的碳酸二苯酯 (DPC) 与二醇的缩聚反应。在本报告的最后一部分,描述了聚甲基丙烯酸苯酯 (PPhMA) 侧链与由 TBZL 催化的醇的酯交换。综述了我们最近对锌酸盐络合物二锂四叔丁基锌酸盐催化的酯交换和聚合的研究。在本报告的第一部分,描述了 TBZL 催化的 ε-己内酯的 ROP。在本报告的第二部分,总结了 TBZL 催化醇与乙酸乙烯酯和羧酸酯的酰化和酯交换。接下来,讨论了 TBZL 催化的碳酸二苯酯 (DPC) 与二醇的缩聚反应。在本报告的最后一部分,描述了聚甲基丙烯酸苯酯 (PPhMA) 侧链与由 TBZL 催化的醇的酯交换。总结了TBZL催化醇与乙酸乙烯酯和羧酸酯的酰化和酯交换反应。接下来,讨论了 TBZL 催化的碳酸二苯酯 (DPC) 与二醇的缩聚反应。在本报告的最后一部分,描述了聚甲基丙烯酸苯酯 (PPhMA) 侧链与由 TBZL 催化的醇的酯交换。总结了TBZL催化醇与乙酸乙烯酯和羧酸酯的酰化和酯交换反应。接下来,讨论了 TBZL 催化的碳酸二苯酯 (DPC) 与二醇的缩聚反应。在本报告的最后一部分,描述了聚甲基丙烯酸苯酯 (PPhMA) 侧链与由 TBZL 催化的醇的酯交换。
更新日期:2020-09-18
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