文献类型：期刊文献

英文题名：Palladium-catalyzed intermolecular asymmetric dearomatizative arylation of indoles and benzofurans

作者：Xi, Yang[1,2];Xu, Youzhi[3];Fan, Linlin[1,2];Wang, Chenchen[1,2];Xia, Tingting[1,2];Huang, Genping[3];Qu, Jingping[1,2];Chen, Yifeng[1,2,4,5]

机构：[1]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn,Key Lab Adv Mat, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Joint Int Res Lab Precis Chem & Mol Engn, Shanghai 200237, Peoples R China;[3]Tianjin Univ, Sch Sci, Dept Chem, Tianjin 300072, Peoples R China;[4]Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Organometall Chem, Shanghai 200032, Peoples R China;[5]Henan Normal Univ, Sch Chem & Chem Engn, Xinxiang 453007, Peoples R China

年份：2025

卷号：11

期号：22

外文期刊名：SCIENCE ADVANCES

收录：;EI(收录号：20252418576052);WOS:【SCI-EXPANDED(收录号:WOS:001499501100025)】；

基金：This work was supported by the Key Project of Science and Technology Innovation 2030 (no. 2023ZD0121002), the National Natural Science Foundation of China (22171079, 22371071, 92356301, T2488302, 22073066, and 22471191), Science and Technology Commission of Shanghai Municipality (grant no. 24DX1400200), the Program of Introducing Talents of Discipline to Universities (B16017), Scientific Committee of Shanghai (21JC1401700), the China Postdoctoral Science Foundation (2023TQ0118), Postdoctoral Fellowship Program of CPSF (GZB20230212), and the Fundamental Research Funds for the Central Universities. We 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：Aromatization - Biosynthesis - Crosslinking - Stereocenters - Stereoselectivity

摘要：Indoles represent one of the most robust and synthetically versatile classes of heteroaromatic compounds. However, the stereoselective conversion of planar indole rings into three-dimensional indoline skeletons bearing multiple stereogenic centers remains a persistent challenge in organic synthesis. Herein, we describe an intermolecular catalytic asymmetric dearomatization of simple indoles via a palladium-catalyzed three-component cross-coupling reaction. By using readily accessible diazonium salts and aromatic boronic acids as arylative reagents under a ligand-swap strategy, this method enables the efficient construction of 2,3-diarylated indolines. Mechanistic studies reveal that the chiral BiOx ligand governs the highly stereoselective migratory insertion of the aryl-palladium intermediate into the indole's C & boxH;C double bond with complete diastereo- and regioselectivity, whereas the achiral fumarate ligand facilitates the reductive elimination step, as corroborated by density functional theory calculations. Furthermore, this protocol is extended to the dearomative diarylation of benzofurans, affording chiral 2,3-dihydrobenzofuran derivatives with high stereocontrol.