{"title":"光电化学镍催化的具有未活化 C/Si-H 键的烯烃的羧基化/硅烷酰化反应","authors":"","doi":"10.1039/d3gc04109c","DOIUrl":null,"url":null,"abstract":"<div><p>Direct and selective installation of two different functional groups into the unsaturated bonds of alkenes constitutes a long-standing goal in organic synthesis. Herein, we first report a photoelectrochemical approach for the carboacylation/silanoylation of alkenes with unactivated alkanes/hydrosilanes <em>via</em> the LMCT process. A number of ketones with high complexity and diversity were rapidly obtained from commercially available materials in an economical and sustainable manner. Furthermore, this protocol can be scaled up to the gram-level. This paired electrocatalysis strategy features excellent regioselectivity, and ample substrate scope, is external-oxidant-free, and features a high resource economy. A series of mechanistic experiments were performed to determine the preferred pathway for the photoelectrochemical Ni(<span>i</span>)/Ni(<span>ii</span>)/Ni(<span>iii</span>) cycles in these transformations.</p></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"26 14","pages":"Pages 8315-8322"},"PeriodicalIF":9.2000,"publicationDate":"2024-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Photoelectrochemical nickel-catalyzed carboacylation/silanoylation of alkenes with unactivated C/Si–H bonds†\",\"authors\":\"\",\"doi\":\"10.1039/d3gc04109c\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Direct and selective installation of two different functional groups into the unsaturated bonds of alkenes constitutes a long-standing goal in organic synthesis. Herein, we first report a photoelectrochemical approach for the carboacylation/silanoylation of alkenes with unactivated alkanes/hydrosilanes <em>via</em> the LMCT process. A number of ketones with high complexity and diversity were rapidly obtained from commercially available materials in an economical and sustainable manner. Furthermore, this protocol can be scaled up to the gram-level. This paired electrocatalysis strategy features excellent regioselectivity, and ample substrate scope, is external-oxidant-free, and features a high resource economy. A series of mechanistic experiments were performed to determine the preferred pathway for the photoelectrochemical Ni(<span>i</span>)/Ni(<span>ii</span>)/Ni(<span>iii</span>) cycles in these transformations.</p></div>\",\"PeriodicalId\":78,\"journal\":{\"name\":\"Green Chemistry\",\"volume\":\"26 14\",\"pages\":\"Pages 8315-8322\"},\"PeriodicalIF\":9.2000,\"publicationDate\":\"2024-07-15\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Green Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/org/science/article/pii/S1463926224006344\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Green Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/org/science/article/pii/S1463926224006344","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Photoelectrochemical nickel-catalyzed carboacylation/silanoylation of alkenes with unactivated C/Si–H bonds†
Direct and selective installation of two different functional groups into the unsaturated bonds of alkenes constitutes a long-standing goal in organic synthesis. Herein, we first report a photoelectrochemical approach for the carboacylation/silanoylation of alkenes with unactivated alkanes/hydrosilanes via the LMCT process. A number of ketones with high complexity and diversity were rapidly obtained from commercially available materials in an economical and sustainable manner. Furthermore, this protocol can be scaled up to the gram-level. This paired electrocatalysis strategy features excellent regioselectivity, and ample substrate scope, is external-oxidant-free, and features a high resource economy. A series of mechanistic experiments were performed to determine the preferred pathway for the photoelectrochemical Ni(i)/Ni(ii)/Ni(iii) cycles in these transformations.
期刊介绍:
Green Chemistry is a journal that provides a unique forum for the publication of innovative research on the development of alternative green and sustainable technologies. The scope of Green Chemistry is based on the definition proposed by Anastas and Warner (Green Chemistry: Theory and Practice, P T Anastas and J C Warner, Oxford University Press, Oxford, 1998), which defines green chemistry as the utilisation of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture and application of chemical products. Green Chemistry aims to reduce the environmental impact of the chemical enterprise by developing a technology base that is inherently non-toxic to living things and the environment. The journal welcomes submissions on all aspects of research relating to this endeavor and publishes original and significant cutting-edge research that is likely to be of wide general appeal. For a work to be published, it must present a significant advance in green chemistry, including a comparison with existing methods and a demonstration of advantages over those methods.