{"title":"Pincer-(NHC)Mn(I) Complex-Catalyzed Selective α-Alkylation of Ketones and Nitriles Using Unactivated Alkenyl Alcohols","authors":"Adarsha Mandal, Manoj Pradhan, Chirantan Mitra, Srabani Nandi, Biswajit Sadhu, Sabuj Kundu","doi":"10.1021/acscatal.4c05889","DOIUrl":null,"url":null,"abstract":"Construction of C–C bonds utilizing challenging alkenyl alcohols employing first-row transition-metal catalysts is an unexplored area. Herein, we report the α-alkylation of ketones and nitriles using unactivated alkenyl alcohols as coupling partners in the presence of a phosphine-free pincer-NHC carbene-Mn(I) complex. This catalytic system was highly effective for the α-alkylation of a wide variety of ketones and acetonitriles having aromatic, heteroaromatic, and aliphatic units in the presence of several reducible functional groups. The practical applicability and synthetic value of this protocol were demonstrated through gram-scale synthesis, evaluation of green chemistry metrics, and functionalization of alkylated products into important molecules. Several control experiments, kinetic studies, and Hammett studies were carried out to understand the reaction mechanism, which was further supported by density functional theory (DFT) calculations.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"29 1","pages":""},"PeriodicalIF":11.3000,"publicationDate":"2024-12-24","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.4c05889","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
Construction of C–C bonds utilizing challenging alkenyl alcohols employing first-row transition-metal catalysts is an unexplored area. Herein, we report the α-alkylation of ketones and nitriles using unactivated alkenyl alcohols as coupling partners in the presence of a phosphine-free pincer-NHC carbene-Mn(I) complex. This catalytic system was highly effective for the α-alkylation of a wide variety of ketones and acetonitriles having aromatic, heteroaromatic, and aliphatic units in the presence of several reducible functional groups. The practical applicability and synthetic value of this protocol were demonstrated through gram-scale synthesis, evaluation of green chemistry metrics, and functionalization of alkylated products into important molecules. Several control experiments, kinetic studies, and Hammett studies were carried out to understand the reaction mechanism, which was further supported by density functional theory (DFT) calculations.
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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