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近年来,钯催化的芳基卤化物和芳基硼酸化合物的羰化偶联反应发展十分迅速。到目前为止,大量硼酸化合物、钯催化剂前体、配体和羰基源被用来合成二芳基甲酮,此类化合物在工业中间体、染料、药剂、天然产物等领域有着广泛的应用。本文从钯催化剂体系、转金属促进剂、羰基源及其应用方面综述了铃木-宫蒲(Suzuki-Miyaura or Suzuki)羰化反应的研究进展。钯催化剂体系从均相和非均相体系两方面介绍,其中均相催化体系包括钯催化剂前驱体、磷配体、氮杂卡宾配体的研究进展;非均相催化体系主要介绍了活性炭、石墨烯、官能化硅胶、四氧化三铁等载体多种固载钯催化剂的应用。特戊酸添加剂可改善转金属化过程,有效加速羰化偶联反应。经典的羰化Suzuki反应一般需要气体钢瓶提供压力较高的一氧化碳气体。尽管近期一些研究实现了常压一氧化碳气球作为羰基供给源,使用一氧化碳释放分子(CO-releasing molecule,CORM)替代剧毒危险的一氧化碳气体可实现更为安全绿色的羰化反应进程。在双管反应器中,有机CORM可控降解释放一氧化碳,为钯催化羰基偶联反应提供CO。在微波辐射下,过渡金属羰基化合物可为羰基化反应原位直接提供CO。
In recent years, palladium-catalyzed carbonylation of aryl halides and aryl boronic acid compounds has developed rapidly. So far, a large number of boric acid compounds, palladium catalyst precursors, ligands and carbonyl sources have been used to synthesize diaryl ketones. These compounds have been widely used in the fields of industrial intermediates, dyes, pharmaceuticals and natural products. This review summarizes the progress in the oxonation of Suzuki-Miyaura or Suzuki from the perspective of palladium catalyst system, transfer metal promoter, carbonyl source and its application. The palladium catalyst system is introduced from both homogeneous and heterogeneous systems. The progress in the research of homogeneous catalyst systems including palladium catalyst precursors, phosphorus ligands and azacarbin ligands is reviewed. The heterogeneous catalytic system mainly introduces activated carbon, graphite Olefin, functionalized silica gel, ferroferric oxide carrier such as a variety of supported palladium catalyst applications. Pivalic acid additives can improve the turn metallization process, effectively accelerate the carbonylation coupling reaction. Classic carbonylation Suzuki reactions generally require gas cylinders to provide higher pressure carbon monoxide gas. Although some recent studies have led to the use of atmospheric carbon monoxide balloons as carbon sources, the use of carbon monoxide (CO) -removing molecules (CORMs) to replace highly toxic carbon monoxide gases can achieve a safer and green carbonylation process. In a two-tube reactor, organic CORM controlled degradation releases carbon monoxide, providing CO for the palladium-catalyzed carbonyl coupling reaction. Under microwave irradiation, the transition metal carbonyl can provide CO directly for the carbonylation reaction in situ.