铑催化芳香羧酸和丙烯酸酯的交叉脱氢偶联反应  

Rhodium-catalyzed ortho-olefination of aromatic acids with acrylates via cross-dehydrogenative coupling

作　　者：赵雪 张子楠 樊娟[1] 石先莹[1] Xue Zhao;Zi-Nan Zhang;Juan Fan;Xian-Ying Shi(Key Laboratory of Syngas Conversion of Shaanxi Province, Key Laboratory for Macromolecular Science of Shaanxi Province, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi'an 710062, China)

机构地区：[1]陕西省合成气转化重点实验室陕西省大分子科学重点实验室陕西师范大学化学化工学院

出　　处：《中国科学：化学》2019年第6期891-898,共8页SCIENTIA SINICA Chimica

基　　金：国家自然科学基金(编号:21572122,21776171)资助项目

摘　　要：烯基芳烃作为重要的有机中间体,被广泛应用于生物、医药、有机合成等领域中.本文以简单易得的芳香羧酸和丙烯酸酯为原料,通过(五甲基环戊二烯基)氯化铑(III)二聚体催化羧基导向的交叉脱氢偶联,实现了羧基邻位碳氢键直接烯基化反应,得到了良好或优异收率的2-烯基取代的游离芳香羧酸.此转化具有反应时间短、反应条件温和、无需任何添加剂、底物适应面广等优点,而且烯基化产物经过简单脱羧反应可合成传统方法难以得到的间位取代烯基化产物.Vinylarenes as key synthetic intermediates have been widely applied in the field of biology, pharmaceutical and organic synthesis. Herein, a rhodium-catalyzed ortho-olefination of aromatic acids with acrylates has been developed for the synthesis of a wide range of ortho-olefinated free aromatic acids in good to excellent yields. The reaction undergoes a removable carboxyl-directed cross-dehydrogenative coupling. Employing simple and readily available starting materials, this process is successfully realized under mild reaction conditions without any additives.Additional features of the method are broad substrate scope and shorter reaction time.

关 键 词：烯基化 羧基导向 交叉脱氢偶联 铑催化 

分 类 号：O621.251[理学—有机化学]