{"title":"Photoredox/Cobalt‐Catalyzed Chemo‐, Regio‐, Diastereo‐ and Enantioselective Reductive Coupling of 1,1‐Disubstituted Allenes and Cyclobutenes","authors":"Qianghui Wu, Zhihan Zhang, Qinglei Chong, Fanke Meng","doi":"10.1002/anie.202416524","DOIUrl":null,"url":null,"abstract":"A dual photoredox/cobalt‐catalyzed protocol for chemo‐, regio‐, diastereo‐ and enantioselective reductive coupling of 1,1‐disubstituted allenes and cyclobutenes through chemo‐, regio‐, diastereo‐ and enantioselective oxidative cyclization followed by stereoselective protonation promoted by a chiral phosphine–cobalt complex is presented. Such process represents an unprecedented reaction pathway for cobalt catalysis that enables selective transformation of the less sterically congested alkenes of 1,1‐disubstituted allenes with cyclobutenes, incorporating a broad scope of tetrasubstituted alkenes into the cyclobutane scaffolds in up to 86% yield, >98:2 chemo‐ and regioselectivity, >98:2 dr and >99.5:0.5 er. Functionalization delivered a variety of enantioenriched cyclobutanes that are otherwise difficult to access. Preliminary mechanistic studies revealed that the reactions proceeded through oxidative cyclization followed by protonation and protonation might be the rate‐determining step.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"25 1","pages":""},"PeriodicalIF":16.1000,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Angewandte Chemie International Edition","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1002/anie.202416524","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
A dual photoredox/cobalt‐catalyzed protocol for chemo‐, regio‐, diastereo‐ and enantioselective reductive coupling of 1,1‐disubstituted allenes and cyclobutenes through chemo‐, regio‐, diastereo‐ and enantioselective oxidative cyclization followed by stereoselective protonation promoted by a chiral phosphine–cobalt complex is presented. Such process represents an unprecedented reaction pathway for cobalt catalysis that enables selective transformation of the less sterically congested alkenes of 1,1‐disubstituted allenes with cyclobutenes, incorporating a broad scope of tetrasubstituted alkenes into the cyclobutane scaffolds in up to 86% yield, >98:2 chemo‐ and regioselectivity, >98:2 dr and >99.5:0.5 er. Functionalization delivered a variety of enantioenriched cyclobutanes that are otherwise difficult to access. Preliminary mechanistic studies revealed that the reactions proceeded through oxidative cyclization followed by protonation and protonation might be the rate‐determining step.
期刊介绍:
Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.