Angel Rentería-Gómez, Rubén O. Torres-Ochoa, Pierre Palamini, Raphaël Simonet-Davin, Qian Wang, Jérôme Waser, Jieping Zhu
{"title":"苄基 C(sp3)-H 氮化：铜催化与铁催化","authors":"Angel Rentería-Gómez, Rubén O. Torres-Ochoa, Pierre Palamini, Raphaël Simonet-Davin, Qian Wang, Jérôme Waser, Jieping Zhu","doi":"10.1002/hlca.202400004","DOIUrl":null,"url":null,"abstract":"<p>The generation of benzylic radicals through hydrogen atom abstraction (HAT) has been a recent research focus and various C(sp<sup>3</sup>)−H bond functionalization protocols have been developed relying on this elementary step. We report herein copper- and iron-catalyzed C(sp<sup>3</sup>)−H benzylic azidation reactions using <i>m</i>CPBA and NFSI as oxidant, respectively, and TMSN<sub>3</sub> as azide source. The reaction is thought to be initiated <i>via</i> intermolecular abstraction of benzylic hydrogen by the <i>in situ</i> generated heteroatom-centered radicals. The Fe(OTf)<sub>3</sub>-catalyzed azidation protocol displays good chemoselectivity as it takes place preferentially at the secondary and tertiary benzylic C(sp<sup>3</sup>)−H bonds over the primary benzylic and tertiary aliphatic carbons. Efforts on the development of catalytic enantioselective processes are also documented.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":1.5000,"publicationDate":"2024-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202400004","citationCount":"0","resultStr":"{\"title\":\"Benzylic C(sp3)−H Azidation: Copper vs Iron Catalysis\",\"authors\":\"Angel Rentería-Gómez, Rubén O. Torres-Ochoa, Pierre Palamini, Raphaël Simonet-Davin, Qian Wang, Jérôme Waser, Jieping Zhu\",\"doi\":\"10.1002/hlca.202400004\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>The generation of benzylic radicals through hydrogen atom abstraction (HAT) has been a recent research focus and various C(sp<sup>3</sup>)−H bond functionalization protocols have been developed relying on this elementary step. We report herein copper- and iron-catalyzed C(sp<sup>3</sup>)−H benzylic azidation reactions using <i>m</i>CPBA and NFSI as oxidant, respectively, and TMSN<sub>3</sub> as azide source. The reaction is thought to be initiated <i>via</i> intermolecular abstraction of benzylic hydrogen by the <i>in situ</i> generated heteroatom-centered radicals. The Fe(OTf)<sub>3</sub>-catalyzed azidation protocol displays good chemoselectivity as it takes place preferentially at the secondary and tertiary benzylic C(sp<sup>3</sup>)−H bonds over the primary benzylic and tertiary aliphatic carbons. Efforts on the development of catalytic enantioselective processes are also documented.</p>\",\"PeriodicalId\":12842,\"journal\":{\"name\":\"Helvetica Chimica Acta\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":1.5000,\"publicationDate\":\"2024-02-09\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202400004\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Helvetica Chimica Acta\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/hlca.202400004\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Helvetica Chimica Acta","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/hlca.202400004","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Benzylic C(sp3)−H Azidation: Copper vs Iron Catalysis
The generation of benzylic radicals through hydrogen atom abstraction (HAT) has been a recent research focus and various C(sp3)−H bond functionalization protocols have been developed relying on this elementary step. We report herein copper- and iron-catalyzed C(sp3)−H benzylic azidation reactions using mCPBA and NFSI as oxidant, respectively, and TMSN3 as azide source. The reaction is thought to be initiated via intermolecular abstraction of benzylic hydrogen by the in situ generated heteroatom-centered radicals. The Fe(OTf)3-catalyzed azidation protocol displays good chemoselectivity as it takes place preferentially at the secondary and tertiary benzylic C(sp3)−H bonds over the primary benzylic and tertiary aliphatic carbons. Efforts on the development of catalytic enantioselective processes are also documented.
期刊介绍：
Helvetica Chimica Acta, founded by the Swiss Chemical Society in 1917, is a monthly multidisciplinary journal dedicated to the dissemination of knowledge in all disciplines of chemistry (organic, inorganic, physical, technical, theoretical and analytical chemistry) as well as research at the interface with other sciences, where molecular aspects are key to the findings. Helvetica Chimica Acta is committed to the publication of original, high quality papers at the frontier of scientific research. All contributions will be peer reviewed with the highest possible standards and published within 3 months of receipt, with no restriction on the length of the papers and in full color.
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号
