文献类型：期刊文献

英文题名：Iron-Catalyzed Asymmetric Cross-Electrophile Alkylation of Imines

作者：Bai, Jiahao[1,2];Wang, Qinglin[1,2];Zhao, Wenyu[1,2];Shen, Yiwen[1,2];Xin, Yuquan[1,2];Wu, Xianqing[1,2];Qu, Jingping[1,2];Chen, Yifeng[1,2,3,4]

机构：[1]East China Univ Sci & Technol, Sch Chem & Mol Engn, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn,Joint Int Res Lab Precis Chem, Shanghai 200237, Peoples R China;[3]Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Organometall Chem, Shanghai 200032, Peoples R China;[4]Henan Normal Univ, Sch Chem & Chem Engn, Xinxiang 453007, Peoples R China

年份：2025

卷号：15

期号：17

起止页码：15112

外文期刊名：ACS CATALYSIS

收录：;EI(收录号：20255119734564);WOS:【SCI-EXPANDED(收录号:WOS:001551129100001)】；

基金：This work was supported by National Natural Science Foundation of China (22171079, 22371071, 92356301, 2240011806), Science and Technology Commission of Shanghai Municipality (grant no. 24DX1400200), the Program of Introducing Talents of Discipline to Universities (B16017), Sinopec Seeding Program (C0607-0876), Shanghai Sailing Program (23YF1408800) and the Fundamental Research Funds for the Central Universities. The authors thank the Analysis and Testing Center of East China University of Science and Technology for help with NMR and HRMS analysis.

语种：英文

外文关键词：iron; cross-electrophile coupling; chiral aminoacid derivatives; asymmetric catalysis; additionreaction

摘要：Transition metal-catalyzed asymmetric cross-electrophile coupling has emerged as a synthetically useful strategy for the stereoselective construction of a carbon-carbon bond. Herein, we report an iron-catalyzed enantioselective cross-electrophile alkylation of alpha-imino esters with unactivated alkyl halides by employing a chiral NPN ligand. This method delivers alpha-tetrasubstituted amino esters in high yields (up to 93%) and enantioselectivity (up to 97:3 er), accommodating diverse substrates, including primary, secondary, and tertiary alkyl iodides, with broad functional group tolerance. The system is extended to asymmetric benzylation using benzyl chlorides, yielding chiral phenylalanine derivatives bearing quaternary stereocenters (up to 97.5:2.5 er), including bioactive motifs. Mechanistic studies suggest alkyl radical intermediates and a low-valent iron catalytic cycle initiated by a single-electron transfer.