配体促进下铜催化的由醛制备过酸叔丁酯及烯丙酯的反应研究  

Ligand-Triggered,Copper Catalyzed Synthesis of Peresters and Allylic Ester from Aldehydes

作　　者：许定健 孟力陈 徐航[1] 姚小泉[1] 

机构地区：[1]南京航空航天大学材料科学与技术学院应用化学系,南京210016

出　　处：《有机化学》2017年第5期1205-1212,共8页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(Nos.21472092;21172107);江苏高校优势学科建设工程资助项目~~

摘　　要：以碘化亚铜为催化剂、2,2'-联吡啶为配体,发展了一种高效、温和且无溶剂参与的催化醛的C—H键活化、与过氧化叔丁醇(TBHP)反应生成过酸酯化合物的反应体系.在该催化体系中,双齿氮配体的加入显著增强了Cu(I)催化剂的催化活性,对该反应起到了关键的开关作用.与文献报道相比,该反应体系反应条件温和、时间短、无需溶剂且底物适应性优良.在此基础上,以上述反应混合物直接与环己烯反应,在较低温度下成功实现了烯丙酯的"一锅法"串联合成.A copper iodide catalyzed reaction of aldehydes and t-butyl hydroperoxide （TBHP） was developed for the synthesis of peresters in the presence of bipyridine ligand under mild and neat conditions. The addition of bipyridine ligand increased the catalytic activities of copper catalyst significantly and triggered the reaction, The reaction showed good tolerance to various substrates, and good to excellent yields were obtained. Furthermore, a one-pot synthesis of allylic esters was also achieved by the addition of cyclohexene to the reaction mixture under neat condition at relative lower temperature.

关 键 词：铜催化 氮配体 C—H活化 过酸酯 烯丙基酯 一锅法合成 无溶剂 

分 类 号：O623.624[理学—有机化学]