{"title":"引导无基团镍催化未活化烯烃二烷基化的均聚取代方法","authors":"Fei Cong, Jun Wei Ng, Ming Joo Koh","doi":"10.1055/a-2352-4902","DOIUrl":null,"url":null,"abstract":"<p>The selective construction of two C(sp<sup>3</sup>)–C(sp<sup>3</sup>) bonds through trimolecular cross-coupling of unactivated alkenes remains one of the most difficult challenges in organic synthesis. Despite previous advances in metal-catalyzed coupling for the dicarbofunctionalization of alkenes, dialkylation is still problematic due to the instability of the requisite metal–alkyl intermediate, which undergoes facile β-hydride elimination or protodemetalation. Recently, our group was successful in developing a bimolecular homolytic substitution (S<sub>H</sub>2) strategy that circumvents metal–alkyl side reactions and accomplishes the challenging cross-coupling of metal–alkyl intermediates with alkyl radicals in the absence of a directing auxiliary, permitting a highly regioselective dialkylation of unactivated alkenes.</p> <p>1\tIntroduction</p> <p>2 Nickel-Catalyzed Dicarbofunctionalization of Unactivated Alkenes</p> <p>3\tNickel-Catalyzed Dialkylation of Unactivated Alkenes</p> <p>4 Conclusions and Perspectives</p> ","PeriodicalId":22319,"journal":{"name":"Synlett","volume":"65 1","pages":""},"PeriodicalIF":1.7000,"publicationDate":"2024-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"A Homolytic Substitution Approach for Directing Group-Free Nickel-Catalyzed Dialkylation of Unactivated Alkenes\",\"authors\":\"Fei Cong, Jun Wei Ng, Ming Joo Koh\",\"doi\":\"10.1055/a-2352-4902\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>The selective construction of two C(sp<sup>3</sup>)–C(sp<sup>3</sup>) bonds through trimolecular cross-coupling of unactivated alkenes remains one of the most difficult challenges in organic synthesis. Despite previous advances in metal-catalyzed coupling for the dicarbofunctionalization of alkenes, dialkylation is still problematic due to the instability of the requisite metal–alkyl intermediate, which undergoes facile β-hydride elimination or protodemetalation. Recently, our group was successful in developing a bimolecular homolytic substitution (S<sub>H</sub>2) strategy that circumvents metal–alkyl side reactions and accomplishes the challenging cross-coupling of metal–alkyl intermediates with alkyl radicals in the absence of a directing auxiliary, permitting a highly regioselective dialkylation of unactivated alkenes.</p> <p>1\\tIntroduction</p> <p>2 Nickel-Catalyzed Dicarbofunctionalization of Unactivated Alkenes</p> <p>3\\tNickel-Catalyzed Dialkylation of Unactivated Alkenes</p> <p>4 Conclusions and Perspectives</p> \",\"PeriodicalId\":22319,\"journal\":{\"name\":\"Synlett\",\"volume\":\"65 1\",\"pages\":\"\"},\"PeriodicalIF\":1.7000,\"publicationDate\":\"2024-07-15\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Synlett\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1055/a-2352-4902\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, ORGANIC\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Synlett","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1055/a-2352-4902","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
A Homolytic Substitution Approach for Directing Group-Free Nickel-Catalyzed Dialkylation of Unactivated Alkenes
The selective construction of two C(sp3)–C(sp3) bonds through trimolecular cross-coupling of unactivated alkenes remains one of the most difficult challenges in organic synthesis. Despite previous advances in metal-catalyzed coupling for the dicarbofunctionalization of alkenes, dialkylation is still problematic due to the instability of the requisite metal–alkyl intermediate, which undergoes facile β-hydride elimination or protodemetalation. Recently, our group was successful in developing a bimolecular homolytic substitution (SH2) strategy that circumvents metal–alkyl side reactions and accomplishes the challenging cross-coupling of metal–alkyl intermediates with alkyl radicals in the absence of a directing auxiliary, permitting a highly regioselective dialkylation of unactivated alkenes.
1 Introduction
2 Nickel-Catalyzed Dicarbofunctionalization of Unactivated Alkenes
3 Nickel-Catalyzed Dialkylation of Unactivated Alkenes
期刊介绍:
SYNLETT is an international journal reporting research results and current trends in chemical synthesis in short personalized reviews and preliminary communications. It covers all fields of scientific endeavor that involve organic synthesis, including catalysis, organometallic, medicinal, biological, and photochemistry, but also related disciplines and offers the possibility to publish scientific primary data.