{"title":"Ni-Catalyzed Enantioconvergent Kumada–Corriu Cross-Coupling between β-Bromostyrenes and Secondary Grignard Reagents: Reaction Development, Scope and Mechanistic Investigations","authors":"Kaidi Li, Baptiste Leforestier, Amalia I. Poblador-Bahamonde, Céline Besnard, Laure Guénée, Svetlana Kucher, Clément Mazet","doi":"10.1021/acscatal.4c06360","DOIUrl":null,"url":null,"abstract":"A Ni-catalyzed enantioconvergent cross-coupling between β-bromostyrenes and secondary Grignard reagents is reported. This C(sp<sup>2</sup>)–C(sp<sup>3</sup>) cross-coupling is applicable to a broad range of electrophilic and nucleophilic partners and affords the products in good to high levels of enantio-induction. Experimental mechanistic investigations revealed an unexpected binding mode of the chiral (P,N) ligand and support a radical rebound mechanism involving in-cage radicals. Kinetic experiments provide evidence for an off-cycle resting state featuring dinuclear species. Computational analyses are in line with this hypothesis and coherent with a catalytic cycle proceeding via a Ni(I)/Ni(III) manifold. They further suggest an enantio-determining radical capture event and shed light on the origin of the Dynamic Kinetic Resolution process.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"89 1","pages":""},"PeriodicalIF":11.3000,"publicationDate":"2024-12-18","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.4c06360","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
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Abstract
A Ni-catalyzed enantioconvergent cross-coupling between β-bromostyrenes and secondary Grignard reagents is reported. This C(sp2)–C(sp3) cross-coupling is applicable to a broad range of electrophilic and nucleophilic partners and affords the products in good to high levels of enantio-induction. Experimental mechanistic investigations revealed an unexpected binding mode of the chiral (P,N) ligand and support a radical rebound mechanism involving in-cage radicals. Kinetic experiments provide evidence for an off-cycle resting state featuring dinuclear species. Computational analyses are in line with this hypothesis and coherent with a catalytic cycle proceeding via a Ni(I)/Ni(III) manifold. They further suggest an enantio-determining radical capture event and shed light on the origin of the Dynamic Kinetic Resolution process.
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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