电子供体-受体(EDA)复合物驱动的N-α位C—H键活化  

Electron Donor-Acceptor (EDA) Complex-Driven Activation of N-α C—H Bonds

作　　者：杨俊峰 赵艳秋[1] 时磊[1] Junfeng Yang;Yanqiu Zhao;Lei Shi(School of Chemistry,Dalian University of Technology,Dalian 116024)

机构地区：[1]大连理工大学化学学院,大连116024

出　　处：《有机化学》2025年第2期559-573,共15页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.21772195);中央高校基础研究基金(No.DUT22QN213)资助项目。

摘　　要：由电子供体-电子受体(EDA)形成的EDA复合物正在引发一个又一个神奇的光化学反应.在可见光照射下, EDA复合物会发生单电子转移(SET)过程,电子从供体转移向电子受体产生自由基阴阳离子对并引发后续反应.除了光作为外部能量来源,这一策略无需额外的光催化剂,反应条件温和,使得这一体系能够兼容大多数底物.胺类化合物特别是氮杂芳烃和脂肪胺作为富电子底物,在近年来已被广泛用于EDA复合物中的电子供体.并且,这类EDA复合物引发的反应中间体具有可预测性和位点选择性,在形成EDA复合物后N-α位具有独特的反应性质,并被用于合成复杂的含氮有机分子.综述了含氮化合物及烷基胺作为EDA电子供体来构建N-α位C—X键(X=C, N)的光化学反应,并对该领域的发展进行了展望.Electron donor-acceptor (EDA) complexes formed by electron donors and electron acceptors are triggering many amazing photochemical reactions. Under visible light irradiation, the EDA complexes undergo a single electron transfer (SET) process, in which electrons are transferred from the donor to the electron acceptor to create free radical anion-cation pairs and initiate subsequent reactions. This strategy does not require an additional photocatalyst under mild reaction conditions with light as an external energy source, making this system compatible well with most substrates. Amines, such as aza-aromatics and aliphatic amines, have been widely used as electron-rich substrates as electron donors in EDA complexes in recent years. Moreover, the reaction intermediates initiated by these EDA complexes are predictable and site-selective, with unique reactive properties at the N-α position after the formation of EDA complexes, and have been used in the synthesis of complex nitrogen-containing organic molecules. The photochemical reactions of nitrogen-containing aromatics and amines as EDA electron donors for the construction of C—X bonds (X=C, N) at the N-α position are reviewed, and an outlook for the development of this field is provided.

关 键 词：电子供体-电子受体(EDA)复合物 光化学 自由基 胺类化合物 C—H键活化 

分 类 号：O621.25[理学—有机化学]