Universal Suzuki–Miyaura Catalyst-Transfer Polymerization for Precision Synthesis of Strong Donor/Acceptor-Based Conjugated Polymers and Their Sequence Engineering
作者:Jaeho Lee、Hwangseok Kim、Hyunwoo Park、Taehyun Kim、Soon-Hyeok Hwang、Daye Seo、Taek Dong Chung、Tae-Lim Choi
DOI:10.1021/jacs.1c05080
日期:2021.7.28
Catalyst-transfer polymerization has revolutionized the field of polymer synthesis due to its living character, but for a given catalyst system, the polymer scope is rather narrow. Herein we report a highly efficient Suzuki–Miyaura catalyst-transfer polymerization (SCTP) that covers a wide range of monomers from electron-rich (donor, D) to electron-deficient (acceptor, A) (hetero)arenes by rationally
催化剂转移聚合因其活性特性而彻底改变了聚合物合成领域,但对于给定的催化剂体系,聚合物范围相当狭窄。在此,我们报告了一种高效的 Suzuki-Miyaura 催化剂转移聚合(SCTP),通过合理设计硼酸酯单体,涵盖从富电子(供体,D)到缺电子(受体,A)(杂)芳烃的广泛单体并使用市售的 Buchwald RuPhos 和 SPhos Pd G3 预催化剂。最初,我们通过引入新的硼酸盐,例如 4,4,8,8 优化了 3,4-丙烯二氧噻吩 (ProDOT)、苯并三唑 (BTz)、喹喔啉 (QX) 和 2,3-二苯基喹喔啉 (QXPh) 的受控聚合-四甲基-1,3,6,2-二氧杂硼烷及其N-苄基化衍生物,以调节单体的反应性和稳定性。结果,PProDOT、PBTz、PQX 和 PQXPh以优异的产率 (>85%)制备,具有受控的分子量和窄分散性 ( ± <1.29)。聚合物结构的详细研究使用1H