Photoinduced generation of alkyl and phthalimide nitrogen radicals from N-hydroxyphthalimide esters for the synthesis of benzophenone-type bioisosteres  

作　　者：Fei Li Jianyang Dong Huijuan Liao Jiayi Dang Xuechen Zhou Yuying Wang Chenya Wang Qin Jiang Gang Li Dong Xue 

机构地区：[1]Key Laboratory of Applied Surface and Colloid Chemistry,Ministry of Education and School of Chemistry and Chemical Engineering,Shaanxi Normal University,Xi’an 710119,China

出　　处：《Science China Chemistry》2024年第10期3389-3396,共8页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China(22171174);the Fundamental Research Funds for the Central Universities(GK202207015,GK202304033,GK202401008);the Innovation Capability Support Program of Shaanxi(2023-CX-TD-28);the Fundamental Science Research Project of Shaanxi for Chemistry,Biology(22JHZ002);the Natural Science Foundation of Shaanxi Province(2023-JC-YB-100);the China Postdoctoral Science Foundation(2023M732165);the Shaanxi Province Postdoctoral Science Foundation(2023BSHYDZZ107);the Young Talent Fund of Association for Science and Technology in Shaanxi,China(20240606)。

摘　　要：N-Hydroxyphthalimide(NHPI)esters have emerged as powerful sources of alkyl radicals generated by single-electron transfer,but homolysis of NHPI ester to produce an alkyl radical and a phthalimide nitrogen radical is still in its infancy.In this study,we developed a light-induced method for generation of alkyl and phthalimide nitrogen radicals from NHPI esters and subsequent reactions of the radicals with[1.1.1]propellane and aryl aldehydes for rapid generation of bicycle[1.1.1]pentane ketones.This method does not require metals or photosensitizers,features a broad substrate scope(90 examples)and excellent functional group tolerance,and can be used for the functionalization of structurally complex natural products and drugs.Mechanistic investigations indicate that the reaction involves photoinduced homolytic cleavage of the Cs_(2)CO_(3)-NHPI ester complex to produce alkyl and phthalimide nitrogen radicals and subsequent hydrogen atom transfer between the phthalimide nitrogen radical and the aldehyde to generate an acyl radical.

关 键 词：phthalimide nitrogen radicals aryl aldehydes hydrogen atom transfer bicycle[1.1.1]pentane ketones BIOISOSTERES 

分 类 号：O621.3[理学—有机化学]