{"title":"Construction of Chiral C2-Quaternary Indolines via Palladium-Catalyzed Decarboxylative Asymmetric Amination","authors":"Mingjun Lv, Xinhui Yu, Jitian Liu, Xiaoxun Li","doi":"10.1021/acscatal.4c05763","DOIUrl":null,"url":null,"abstract":"The catalytic asymmetric synthesis of functionalized C2-quaternary indoline scaffolds has garnered significant attention in organic synthesis and drug discovery due to the inherent challenges and potential applications. Herein, we present a facile approach utilizing a Pd-catalyzed intramolecular decarboxylative asymmetric amination of vinyl benzoxazepinones, leading to the efficient construction of challenging chiral 2-vinyl-2-aryl/alkyl indoline frameworks in good yields with high enantioselectivities (>50 examples, up to 83% yield and 97% ee). Furthermore, these chiral indolines can be readily scaled up and further modified to access complex polycyclic indoline structures. We also synthesized several indoline-based ligands that exhibit promising efficiency as chiral catalysts in asymmetric reactions. Computational studies provided insight into the inner-sphere asymmetric amination mechanism.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"35 1","pages":""},"PeriodicalIF":11.3000,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Catalysis ","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acscatal.4c05763","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
The catalytic asymmetric synthesis of functionalized C2-quaternary indoline scaffolds has garnered significant attention in organic synthesis and drug discovery due to the inherent challenges and potential applications. Herein, we present a facile approach utilizing a Pd-catalyzed intramolecular decarboxylative asymmetric amination of vinyl benzoxazepinones, leading to the efficient construction of challenging chiral 2-vinyl-2-aryl/alkyl indoline frameworks in good yields with high enantioselectivities (>50 examples, up to 83% yield and 97% ee). Furthermore, these chiral indolines can be readily scaled up and further modified to access complex polycyclic indoline structures. We also synthesized several indoline-based ligands that exhibit promising efficiency as chiral catalysts in asymmetric reactions. Computational studies provided insight into the inner-sphere asymmetric amination mechanism.
期刊介绍：
ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels.
The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.
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