铃木-宫浦羰化反应在合成二芳基甲酮中的应用  

Suzuki-Miyaura Carbonylative Reaction in the Synthesis of Biaryl Ketones

作　　者：朱壮丽 张伟强[1] 高子伟[1] 

机构地区：[1]教育部表面与胶体化学重点实验室陕西师范大学化学化工学院,西安710100

出　　处：《化学进展》2016年第11期1626-1633,共8页Progress in Chemistry

基　　金：国家自然科学基金项目(No.21271124;21272186;21371112;21446014);111计划(B14041);中央高校基本科研基金项目(No.GK201501005;GK201503029;2016CSY002);国家教育部博士点专项基金(No.20120202120005);长江学者与创新团队发展计划(No.IRT_14R33)资助~~

摘　　要：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。Palladium-catalyzed carbonylative coupling reactions of aromatic halides and aryl boronic acids have been rapidly developed during recent years. Nowadays, a plethora of boronic acid compounds, palladium catalyst precursors and CO resources are available for the synthesis of diaryl ketones, which are important intermediates in the manufacture of dyes, pharmaceuticals and natural products. In this review, we summarize the development of these carbonylative reactions with aspects of palladium catalyst system, transmetallation, alternative CO resources and application. The progress on palladium catalyst system covers both homogeneous and heterogeneous reaction systems. A large variety of palladium catalyst precursors, phosphine ligands, HNC ligands in different solvents are discussed in detail, whilst oalladium catalysts immobilized nn aetiv earhnngraphene, ligand functionalized silica gel, Fe304 are also included. Notably, the improvement in the transmetallation process is potentially valuable of achieving efficient carbonylative coupling reaction, in which the pivalic acid additive is found to accelerate the carbonylative coupling. In the classic carbonylative procedure, CO gas from high pressurized cylinders is required in palladium catalyzed Suzuki carbonylative reaction. Although few innovations using CO balloon is reported, the replace of odorless and toxic CO gas by carbon monoxide release molecules （CORM） are highly desirable and offered a safer and greener carbonylation process. To supply CO for palladium-catalyzed carbonylative coupling reaction, various organic CORMs releases CO via controllable degradation in two-chamber system. Transition metal carbonyl compounds as solid CORM directly provides CO under microwave radiation.

关 键 词：二芳基甲酮 合成 铃木-宫浦反应 羰化 

分 类 号：O621.3[理学—有机化学]