Masaya Azami, Michinori Sumimoto, Reika Nakamura, T. Murafuji, Shin Kamijo
{"title":"光诱导芳基酮通过协同同溶芳香族取代催化醚和 N-叔丁氧羰基胺杂原子上的 C(sp3)-H 键的苯化作用","authors":"Masaya Azami, Michinori Sumimoto, Reika Nakamura, T. Murafuji, Shin Kamijo","doi":"10.1055/a-2338-4243","DOIUrl":null,"url":null,"abstract":"A single-step phenylation at the non-acidic C(sp3)–H bond attached to the heteroatom of ethers and N-Boc-amines has been achieved using photoexcited 4-benzoylpyridine as a hydrogen atom transfer (HAT) catalyst. The design of electron-deficient (trifluoromethylsulfonyl)benzene derivatives, as a phenyl precursor, was critical to realizing the present transformation. Moreover, the DFT calculation indicated that the present transformation proceeds via a concerted homolytic aromatic substitution rather than via a stepwise one involving the formation of a cyclohexadienyl radical intermediate.","PeriodicalId":501298,"journal":{"name":"Synthesis","volume":"3 9","pages":""},"PeriodicalIF":0.0000,"publicationDate":"2024-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Photoinduced Aryl Ketone-Catalyzed Phenylation of C(sp3)–H Bonds Attached to the Heteroatom of Ethers and N-Boc-amines via Concerted Homolytic Aromatic Substitution\",\"authors\":\"Masaya Azami, Michinori Sumimoto, Reika Nakamura, T. Murafuji, Shin Kamijo\",\"doi\":\"10.1055/a-2338-4243\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"A single-step phenylation at the non-acidic C(sp3)–H bond attached to the heteroatom of ethers and N-Boc-amines has been achieved using photoexcited 4-benzoylpyridine as a hydrogen atom transfer (HAT) catalyst. The design of electron-deficient (trifluoromethylsulfonyl)benzene derivatives, as a phenyl precursor, was critical to realizing the present transformation. Moreover, the DFT calculation indicated that the present transformation proceeds via a concerted homolytic aromatic substitution rather than via a stepwise one involving the formation of a cyclohexadienyl radical intermediate.\",\"PeriodicalId\":501298,\"journal\":{\"name\":\"Synthesis\",\"volume\":\"3 9\",\"pages\":\"\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2024-06-04\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Synthesis\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.1055/a-2338-4243\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Synthesis","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1055/a-2338-4243","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
Photoinduced Aryl Ketone-Catalyzed Phenylation of C(sp3)–H Bonds Attached to the Heteroatom of Ethers and N-Boc-amines via Concerted Homolytic Aromatic Substitution
A single-step phenylation at the non-acidic C(sp3)–H bond attached to the heteroatom of ethers and N-Boc-amines has been achieved using photoexcited 4-benzoylpyridine as a hydrogen atom transfer (HAT) catalyst. The design of electron-deficient (trifluoromethylsulfonyl)benzene derivatives, as a phenyl precursor, was critical to realizing the present transformation. Moreover, the DFT calculation indicated that the present transformation proceeds via a concerted homolytic aromatic substitution rather than via a stepwise one involving the formation of a cyclohexadienyl radical intermediate.