铱催化C—H键活化硼化及其转化合成聚三氟苯乙烯衍生物

Synthesis of Polytrifluorostyrene Derivatives via Iridium-Catalyzed C—H Activation/Borylation and Subsequent Transformation

在1,5-环辛二烯氯化铱(I)二聚体([IrCl(COD)]2)和4,4′-二叔丁基-2,2’-联吡啶(dtbpy)的催化作用下,成功实现了聚三氟苯乙烯(PTFS)的C—H键活化硼化反应。通过调节联硼酸频那醇酯与PTFS中重复单元的物质的量之比,可以有效地控制PTFS中硼酸酯基团的含量。然后通过聚三氟苯乙烯(PTFS-Bpin)与含羰基或砜基的溴代芳烃间的Suzuki-Miyaura偶联反应,将含羰基或砜基的芳基侧链引入到PTFS中。采用核磁共振(1 H-NMR、11 B-NMR和13 C-NMR)、凝胶渗透色谱(GPC)、差示扫描量热分析(DSC)和热重分析(TG)等测试分析了聚合物的结构和性质。结果表明:经硼化及偶联反应修饰后的PTFS具有良好的溶解性和热稳定性,硼酸酯官能团的存在为向PTFS中进一步引入其他功能性侧链提供了可能。

Novel polytrifluorostyrene （PTFS） derivatives with pendant pinacolboronate groups （PTFSBpin） were successfully prepared via aromatic C--H activation/borylation reactions in the presence of chloro（1,5-cyclooctadiene） iridium （I） dimer （[ IrCl （COD）]2） and 4,4 ＇-di-tert-butyl bipyridine （dtbpy）. The contents of pinaeolboronate groups incorporated into the PTFS were effectively controlled by adjusting the mole ratios of boron reagents related to polymer repeating units. The Suzuki-Miyaura coupling reactions between PTFS-Bpin and aryl bromide containing carbonyl group or sulfonyl group were conducted. The structures and properties of the resulted polymers were analyzed by NMR（^1H NMR, ^11B-NMR and ^13C-NMR）, Gel Permeation Chromatography （GPC）, Differential Scanning Calorimetry （DSC）, and Thermal Gravimetric analysis （TG）, etc. Results showed that the side chain modified PTFS possessed good solubility and thermal stability. The existence of boronate group in PTFS made it possible to introduce other functional side chains.