NFSI参与的高效铜催化苄位碳氢键烷氧基化反应  

Highly efficient copper-catalyzed benzylic C–H alkoxylation with NFSI

作　　者：张铖[1] 汪普生 Cheng Zhang;Pu-Sheng Wang(Hefei National Research Center for Physical Sciences at the Microscale and Department of Chemistry,University of Science and Technology of China,Hefei 230026,China)

机构地区：[1]中国科学技术大学化学系,合肥微尺度物质科学国家研究中心,安徽合肥230026

出　　处：《中国科学技术大学学报》2023年第12期8-13,I0002,I0009,共8页JUSTC

基　　金：supported by USTC Research Funds of the Double First-Class Initiative(YD2060002024);Youth Innovation Promotion Association CAS(2020448);National Natur-al Science Foundation of China(22171254);Anhui Provincial Natural Science Foundation(2108085MB58);Start-up Research Fund from University of Science and Technology of China(KY2060000216).

摘　　要：本文报道了一种铜催化苄位碳氢键烷氧基化反应,该反应在不需添加牺牲还原剂的条件下进行。机理研究揭示了从醋酸铜、N-氟代双苯磺酰胺和甲醇生成活性一价铜物种的新途径,其中适当用量的铜催化剂能够平衡苄位碳氢键烷氧基化反应和苄基醚产物过度氧化的反应速率,从而获得最佳收率。A sacrificial reductant-free copper-catalyzed benzylic C–H alkoxylation with N-Fluorobenzenesulfonimide(NFSI)was reported.Mechanistic studies suggested a novel pathway for the generation of active CuI species from Cu(OAc)2,NFSI and MeOH.A proper loading amount of copper catalyst was found to balance the reaction rates of benzylic C–H alkoxylation and overoxidation of benzyl ether to exhibit the best performance.

关 键 词：碳氢活化 氢原子转移 烷氧基化 醇 铜 自由基 

分 类 号：O621.3[理学—有机化学]