King Eric R, Tropp Joshua, Eedugurala Naresh, Gonce Lauren E, Stanciu Sonia, Azoulay Jason D
School of Polymer Science and Engineering, The University of Southern Mississippi, 118 College Drive #5050, Hattiesburg, MS, 39406, USA.
Angew Chem Int Ed Engl. 2020 Dec 1;59(49):21971-21975. doi: 10.1002/anie.202011426. Epub 2020 Nov 3.
Homogeneous gold (Au) complexes have demonstrated tremendous utility in modern organic chemistry; however, their application for the synthesis of polymers remains rare. Herein, we demonstrate the first catalytic application of Au complexes toward the polycondensation of alkyne-containing comonomers and heteroarene nucleophiles. Polymerization occurs through successive intermolecular hydroarylation reactions to produce high molecular weight aromatic copolymers with 1,1-disubstituted alkene backbone linkages. Clear correlations between the rate and degree of polymerization (DP) were established based on catalyst structure and counterion pairing, thus enabling polymerization reactions that proceeded with remarkable efficiency, high reactivity, and exceptional DPs. The reactivity is broad in scope, enabling the copolymerization of highly functionalized aromatic and aliphatic monomers. These results highlight the untapped utility of Au catalysis in providing access to new macromolecular constructs.
均相金（Au）配合物在现代有机化学中已展现出巨大的实用性；然而，它们在聚合物合成中的应用仍然很少。在此，我们展示了金配合物首次催化含炔共聚单体与杂芳烃亲核试剂的缩聚反应。聚合反应通过连续的分子间氢芳基化反应进行，以生成具有1,1-二取代烯烃主链连接的高分子量芳族共聚物。基于催化剂结构和抗衡离子配对，建立了聚合速率与聚合度（DP）之间的明确相关性，从而实现了具有显著效率、高反应活性和优异聚合度的聚合反应。反应活性范围广泛，能够使高度官能化的芳族和脂肪族单体进行共聚。这些结果突出了金催化在获得新型大分子结构方面尚未开发的实用性。
