Abstract

This mini-review deals with the nonstoichiometric Suzuki–Miyaura polycondensation of excess dibromoarylene with arylenediboronic acid (ester) in the presence of t-Bu₃PPd precatalyst and CsF/18-crown-6 as a base. Since t-Bu₃PPd(0), generated from precatalyst with the assistance of base, has a propensity for intramolecular catalyst transfer on the π-electron face of aromatics, successive reaction of dibromoarylene with 2 equivalents of arylenediboronic acid (ester) takes place through intramolecular catalyst transfer of t‑Bu₃PPd(0) on dibromoarylene, affording high-molecular-weight polymer, even though an excess of dibromoarylene is used. High-molecular-weight poly(tetraalkoxy-substituted stilbene), polyphenylene, polyfluorene, poly(thiophene-alt-phenylene), poly(fluorene-alt-benzthiadiazole), poly(phenylene-alt-benzothiadiazle), poly(cyclopentadithiophene-alt-benzothiadiazole), and polyphenylene containing C≡C, N=N, CH₂, CO, N-Bu, O, SO₂ in the backbone have been obtained under nonstoichiometric conditions. The obtained polymers have a boronic acid (ester) moiety at both ends, which can be converted to other functional groups by means of Suzuki–Miyaura coupling reaction with another reagent, oxidation, bromination, and so on. In the synthesis of poly(tetraalkoxy-substituted stilbene), the abnormal nonstoichiometric polycondensation, affording high-molecular-weight polymer with a boronic acid ester moiety at both ends, can be switched to normal nonstoichiometric polycondensation, affording low-molecular-weight polymer with bromine at both ends, simply by the addition of unsubstituted stilbene, which promotes intermolecular catalyst transfer due to catalyst trapping. When at least one of the two monomers has a kinked structure, such as m-dibromophenylene or m-phenylenediboronic acid (ester), many kinds of cyclic polymers can be selectively obtained even under nonstoichiometric conditions.

中文翻译：

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非化学计量的铃木-Miyaura缩聚反应合成芳族聚合物

摘要

此迷你审查用过量dibromoarylene与在存在arylenediboronic酸（酯）的非化学计量铃木-宫浦缩聚优惠吨-Bu ₃ PPD预催化剂和CsF / 18-冠-6的位置。由于吨-Bu ₃ PPD（0），从与碱的帮助下产生的预催化剂，具有用于对芳族化合物的π电子面分子内催化剂转移，与2个当量arylenediboronic酸dibromoarylene的连续反应的倾向（酯）发生通过t -Bu _3的分子内催化剂转移即使使用过量的二溴亚芳基，在二溴亚芳基上的PPd（0）仍可提供高分子量聚合物。高分子量聚（四烷氧基取代的二苯乙烯），聚苯，聚芴，聚（噻吩ALT亚苯基），聚（芴ALT -benzthiadiazole），聚（亚苯基- ALT -benzothiadiazle），聚（cyclopentadithiophene- ALT -苯并噻二唑）和含有C≡C，N = N，CH ₂，CO，N-Bu，O，SO _2的聚苯撑在非化学计量条件下已获得主链上的“α”。所获得的聚合物在两端均具有硼酸（酯）部分，可以通过Suzuki-Miyaura与另一种试剂的偶联反应，氧化，溴化等作用转化为其他官能团。在聚（四烷氧基取代的1,2-二苯乙烯）的合成中，异常的非化学计量缩聚可转换为正常的非化学计量缩聚，从而提供低分子量的聚合物。仅通过添加未取代的1,2-二苯乙烯就可在两端形成溴，从而由于催化剂的捕获而促进分子间催化剂的转移。当两种单体中的至少一种具有扭结结构时，例如m-dibromophenylene或中号-phenylenediboronic酸（酯），许多种环状聚合物的可被选择性地，即使在非化学计量的条件下获得的。