铜(I)催化的非末端烯酰胺的三氟甲基化反应:N-(3,3,3-三氟-2-芳基-1-丙烯基)取代苯甲酰胺的合成  

Copper(I)-Catalyzed Non-terminal Enamides Trifluoromethylation: Flexible Synthesis of N-(3,3,3-Trifluoro-2-arylprop-1-en-1-yl) Substituted Benzamide

作　　者：王清 高克成 邹建平[1] 曾润生[1] Wang Qing;Gao Kecheng;Zou Jianping;Zeng Runsheng.(Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry Chemical Engineering and Materials Science, Soochow University, Suzhou 215123)

机构地区：[1]苏州大学材料与化学化工学部,苏州215123

出　　处：《有机化学》2018年第4期863-870,共8页Chinese Journal of Organic Chemistry

基　　金：江苏省产学研前瞻性联合研究(No.BY2015039-08);国家自然科学基金(No.21472133);江苏省高等学校优势学科基金资助项目~~

摘　　要：以非末端烯酰胺N-芳基乙烯基取代苯甲酰胺和Togni试剂为原料,以二氯乙烷为溶剂,在碘化亚铜等铜盐催化和磷酸氢二钠存在下,90℃反应,简单有效的合成了N-(3,3,3-三氟-2-芳基-1-丙烯基)取代的苯甲酰胺.通过控制实验对反应机理进行了研究,结果表明反应先通过一价铜催化Togni试剂产生三氟甲基自由基,然后三氟甲基自由基选择性地加成到烯酰胺碳碳双键的β位上.A novel CuI-catalyzed trifluoromethylation of non-terminal enamides was investigated. N-Arylvinyl-substituted benzamide reacted with Togni reagent in dichloroethylane to afford N-（3,3,3-trifluoro-2-arylprop-l-en-l-yl） substituted ben- zamide. The reaction proceeded at 90℃ in air atmosphere in the presence of base and ligands. Control experiment shows that the Togni reagent firstly released CF3 radical in the presence of copper（I） salts and CF3 radical selectively added to the car- bon-carbon double bond of r-position ofenamides.

关 键 词：三氟甲基化 Togni试剂 催化剂 烯胺 

分 类 号：O625.6[理学—有机化学]