Essam M. Eliwa , Ahmed H. Bedair , Jean-Pierre Djukic
{"title":"过渡金属催化的 C(sp2/sp3)-H α-氟烯烃化反应:范围、机理和合成应用。","authors":"Essam M. Eliwa , Ahmed H. Bedair , Jean-Pierre Djukic","doi":"10.1039/d4ob01044b","DOIUrl":null,"url":null,"abstract":"<div><p>Organofluorines have a broad range of industrial applications, such as pharmaceuticals, liquid crystal displays (LCDs), solar cells, textiles, and construction coatings, and are used in peptidomimetics, surfactants, refrigerants, anesthetics, and agrochemicals. Among them are versatile monofluoroalkenes that play a crucial role in medicinal and synthetic chemistry. The synthetic strategies for this class of molecules are limited, and prior efforts frequently suffered from poor atom- and step-economies. As a surrogate pathway for traditional cross-coupling transformations, transition metal (TM)-catalyzed C–H direct α-fluoroalkenylation overcomes these obstacles and provides straightforward techniques to access monofluoroalkenes. Nevertheless, substrate scope is still a challenge for catalysis, where <em>gem</em>-bromofluoroalkene synthons are applicable with electronically biased substrates such as azoles, while <em>gem</em>-difluoroalkene-based strategies are limited to substrates containing N-based directing groups. Herein, we review the cutting-edge fluoroalkenylation research for direct synthesis of monofluoroalkenes achieved during the last decade (2013–2023). This review is divided into two main parts: the first part discusses TM-catalyzed direct α-fluoroalkenylation <em>via</em> the merging of C–H activation and C(sp<sup>2</sup>)–Br cleavage strategies using <em>gem</em>-bromofluoroalkenes, and the second part describes the same reaction, albeit with C(sp<sup>2</sup>)–F cleavage of highly explored <em>gem</em>-difluoroolefins. Our review surveys all previously reported monofluoroalkenes in this research area, including their preparation techniques, stereoselectivity, and yield percentages. Furthermore, optimal conditions, reactant scope, mechanistic investigations, synthetic applications, benefits, and drawbacks of each presented methodology are critically discussed.</p></div>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":"22 34","pages":"Pages 6860-6904"},"PeriodicalIF":2.9000,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ob/d4ob01044b?page=search","citationCount":"0","resultStr":"{\"title\":\"Transition metal-catalyzed C(sp2/sp3)–H α-fluoroalkenylation from gem-(bromo/di)fluoroalkenes to monofluoroalkenes: scope, mechanisms, and synthetic applications\",\"authors\":\"Essam M. Eliwa , Ahmed H. Bedair , Jean-Pierre Djukic\",\"doi\":\"10.1039/d4ob01044b\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Organofluorines have a broad range of industrial applications, such as pharmaceuticals, liquid crystal displays (LCDs), solar cells, textiles, and construction coatings, and are used in peptidomimetics, surfactants, refrigerants, anesthetics, and agrochemicals. Among them are versatile monofluoroalkenes that play a crucial role in medicinal and synthetic chemistry. The synthetic strategies for this class of molecules are limited, and prior efforts frequently suffered from poor atom- and step-economies. As a surrogate pathway for traditional cross-coupling transformations, transition metal (TM)-catalyzed C–H direct α-fluoroalkenylation overcomes these obstacles and provides straightforward techniques to access monofluoroalkenes. Nevertheless, substrate scope is still a challenge for catalysis, where <em>gem</em>-bromofluoroalkene synthons are applicable with electronically biased substrates such as azoles, while <em>gem</em>-difluoroalkene-based strategies are limited to substrates containing N-based directing groups. Herein, we review the cutting-edge fluoroalkenylation research for direct synthesis of monofluoroalkenes achieved during the last decade (2013–2023). This review is divided into two main parts: the first part discusses TM-catalyzed direct α-fluoroalkenylation <em>via</em> the merging of C–H activation and C(sp<sup>2</sup>)–Br cleavage strategies using <em>gem</em>-bromofluoroalkenes, and the second part describes the same reaction, albeit with C(sp<sup>2</sup>)–F cleavage of highly explored <em>gem</em>-difluoroolefins. Our review surveys all previously reported monofluoroalkenes in this research area, including their preparation techniques, stereoselectivity, and yield percentages. Furthermore, optimal conditions, reactant scope, mechanistic investigations, synthetic applications, benefits, and drawbacks of each presented methodology are critically discussed.</p></div>\",\"PeriodicalId\":96,\"journal\":{\"name\":\"Organic & Biomolecular Chemistry\",\"volume\":\"22 34\",\"pages\":\"Pages 6860-6904\"},\"PeriodicalIF\":2.9000,\"publicationDate\":\"2024-08-28\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.rsc.org/en/content/articlepdf/2024/ob/d4ob01044b?page=search\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organic & Biomolecular Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/org/science/article/pii/S1477052024007055\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, ORGANIC\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organic & Biomolecular Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/org/science/article/pii/S1477052024007055","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
Transition metal-catalyzed C(sp2/sp3)–H α-fluoroalkenylation from gem-(bromo/di)fluoroalkenes to monofluoroalkenes: scope, mechanisms, and synthetic applications
Organofluorines have a broad range of industrial applications, such as pharmaceuticals, liquid crystal displays (LCDs), solar cells, textiles, and construction coatings, and are used in peptidomimetics, surfactants, refrigerants, anesthetics, and agrochemicals. Among them are versatile monofluoroalkenes that play a crucial role in medicinal and synthetic chemistry. The synthetic strategies for this class of molecules are limited, and prior efforts frequently suffered from poor atom- and step-economies. As a surrogate pathway for traditional cross-coupling transformations, transition metal (TM)-catalyzed C–H direct α-fluoroalkenylation overcomes these obstacles and provides straightforward techniques to access monofluoroalkenes. Nevertheless, substrate scope is still a challenge for catalysis, where gem-bromofluoroalkene synthons are applicable with electronically biased substrates such as azoles, while gem-difluoroalkene-based strategies are limited to substrates containing N-based directing groups. Herein, we review the cutting-edge fluoroalkenylation research for direct synthesis of monofluoroalkenes achieved during the last decade (2013–2023). This review is divided into two main parts: the first part discusses TM-catalyzed direct α-fluoroalkenylation via the merging of C–H activation and C(sp2)–Br cleavage strategies using gem-bromofluoroalkenes, and the second part describes the same reaction, albeit with C(sp2)–F cleavage of highly explored gem-difluoroolefins. Our review surveys all previously reported monofluoroalkenes in this research area, including their preparation techniques, stereoselectivity, and yield percentages. Furthermore, optimal conditions, reactant scope, mechanistic investigations, synthetic applications, benefits, and drawbacks of each presented methodology are critically discussed.
期刊介绍:
Organic & Biomolecular Chemistry is an international journal using integrated research in chemistry-organic chemistry. Founded in 2003 by the Royal Society of Chemistry, the journal is published in Semimonthly issues and has been indexed by SCIE, a leading international database. The journal focuses on the key research and cutting-edge progress in the field of chemistry-organic chemistry, publishes and reports the research results in this field in a timely manner, and is committed to becoming a window and platform for rapid academic exchanges among peers in this field. The journal's impact factor in 2023 is 2.9, and its CiteScore is 5.5.