{"title":"来自互补配对炔烃的游离碳烯","authors":"Qian Xu, Thomas R. Hoye","doi":"10.1038/s41557-024-01550-9","DOIUrl":null,"url":null,"abstract":"Carbenes (R1R2C:) like radicals, arynes and nitrenes constitute an important family of neutral, high-energy, reactive intermediates—fleeting chemical entities that undergo rapid reactions. An alkyne (R3C≡CR4) is a fundamental functional group that houses a high degree of potential energy; however, the substantial kinetic stability of alkynes renders them conveniently handleable as shelf-stable chemical commodities. The ability to generate metal-free carbenes directly from alkynes, fuelled by the high potential (that is, thermodynamic) energy of the latter, would constitute a considerable advance. We report here that this can be achieved simply by warming a mixture of a 2-alkynyl iminoheterocycle (a cyclic compound containing a nucleophilic nitrogen atom) with an electrophilic alkyne. We demonstrate considerable generality for the process: many shelf-stable alkyne electrophiles engage many classes of (2-alkynyl)heterocyclic nucleophiles to produce carbene intermediates that immediately undergo many types of transformations to provide facile and practical access to a diverse array of heterocyclic products. Key mechanistic aspects of the reactions are delineated. Thermal generation of free carbenes with 100% atom economy is rare. Now, it has been shown that this can be achieved by the net [3+2] cycloaddition between many classes of 2-alkynyl iminoheterocycles and electrophilic alkynes. Together with a host of carbene trapping reactions, this method provides facile and versatile access to diverse heterocycle scaffolds.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":null,"pages":null},"PeriodicalIF":19.2000,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Free carbenes from complementarily paired alkynes\",\"authors\":\"Qian Xu, Thomas R. Hoye\",\"doi\":\"10.1038/s41557-024-01550-9\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Carbenes (R1R2C:) like radicals, arynes and nitrenes constitute an important family of neutral, high-energy, reactive intermediates—fleeting chemical entities that undergo rapid reactions. An alkyne (R3C≡CR4) is a fundamental functional group that houses a high degree of potential energy; however, the substantial kinetic stability of alkynes renders them conveniently handleable as shelf-stable chemical commodities. The ability to generate metal-free carbenes directly from alkynes, fuelled by the high potential (that is, thermodynamic) energy of the latter, would constitute a considerable advance. We report here that this can be achieved simply by warming a mixture of a 2-alkynyl iminoheterocycle (a cyclic compound containing a nucleophilic nitrogen atom) with an electrophilic alkyne. We demonstrate considerable generality for the process: many shelf-stable alkyne electrophiles engage many classes of (2-alkynyl)heterocyclic nucleophiles to produce carbene intermediates that immediately undergo many types of transformations to provide facile and practical access to a diverse array of heterocyclic products. Key mechanistic aspects of the reactions are delineated. Thermal generation of free carbenes with 100% atom economy is rare. Now, it has been shown that this can be achieved by the net [3+2] cycloaddition between many classes of 2-alkynyl iminoheterocycles and electrophilic alkynes. Together with a host of carbene trapping reactions, this method provides facile and versatile access to diverse heterocycle scaffolds.\",\"PeriodicalId\":18909,\"journal\":{\"name\":\"Nature chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":19.2000,\"publicationDate\":\"2024-06-25\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Nature chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.nature.com/articles/s41557-024-01550-9\",\"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":"Nature chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.nature.com/articles/s41557-024-01550-9","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Carbenes (R1R2C:) like radicals, arynes and nitrenes constitute an important family of neutral, high-energy, reactive intermediates—fleeting chemical entities that undergo rapid reactions. An alkyne (R3C≡CR4) is a fundamental functional group that houses a high degree of potential energy; however, the substantial kinetic stability of alkynes renders them conveniently handleable as shelf-stable chemical commodities. The ability to generate metal-free carbenes directly from alkynes, fuelled by the high potential (that is, thermodynamic) energy of the latter, would constitute a considerable advance. We report here that this can be achieved simply by warming a mixture of a 2-alkynyl iminoheterocycle (a cyclic compound containing a nucleophilic nitrogen atom) with an electrophilic alkyne. We demonstrate considerable generality for the process: many shelf-stable alkyne electrophiles engage many classes of (2-alkynyl)heterocyclic nucleophiles to produce carbene intermediates that immediately undergo many types of transformations to provide facile and practical access to a diverse array of heterocyclic products. Key mechanistic aspects of the reactions are delineated. Thermal generation of free carbenes with 100% atom economy is rare. Now, it has been shown that this can be achieved by the net [3+2] cycloaddition between many classes of 2-alkynyl iminoheterocycles and electrophilic alkynes. Together with a host of carbene trapping reactions, this method provides facile and versatile access to diverse heterocycle scaffolds.
期刊介绍:
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