2019
DOI: 10.1038/s41467-019-12722-4
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Site-selective remote C(sp3)–H heteroarylation of amides via organic photoredox catalysis

Abstract: Radical translocation processes triggered by nitrogen-centered radicals (NCRs), such as 1,5-hydrogen atom transfers (1,5-HAT), demonstrated by the well-established Hofmann-Löffler-Freytag (HLF) reaction, provide an attractive approach for the controllable and selective functionalization of remote inert C(sp3)–H bonds. Here we report an amidyl radical-triggered site-selective remote C(sp3)–H heteroarylation of amides under organic photoredox conditions. This approach provides a mild and highly regioselective re… Show more

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Cited by 94 publications
(52 citation statements)
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“…We recently became interested in remote C­(sp3)–H functionalization mediated by nitrogen-centered radicals ( N -radicals) under photoredox conditions. , The success of these reactions depends on the generation of N -radicals from hydroxylamine derivatives and subsequent radical translocation giving the alkyl radicals. Inspired by these N -radical-mediated remote C­(sp3)–H functionalizations, as well as the aforementioned HAT-mediated desaturation, we would like to report a photoinduced and Pd-catalyzed remote desaturation of amide derivatives mediated by N -radicals giving unsaturated amides (Figure d).…”
mentioning
confidence: 99%
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“…We recently became interested in remote C­(sp3)–H functionalization mediated by nitrogen-centered radicals ( N -radicals) under photoredox conditions. , The success of these reactions depends on the generation of N -radicals from hydroxylamine derivatives and subsequent radical translocation giving the alkyl radicals. Inspired by these N -radical-mediated remote C­(sp3)–H functionalizations, as well as the aforementioned HAT-mediated desaturation, we would like to report a photoinduced and Pd-catalyzed remote desaturation of amide derivatives mediated by N -radicals giving unsaturated amides (Figure d).…”
mentioning
confidence: 99%
“…Based on the aforementioned mechanistic studies and relevant literatures a proposed mechanism for this reaction is presented in Figure . Initially, the Pd(0) complex is excited by visible light, which is quenched by an O -acyl hydroxamide 1a .…”
mentioning
confidence: 99%
“…In 2019, the Yu group demonstrated N-centered radical triggered unconventional remote C(sp 3 )À H functionalization of aliphatic amides (29) via 1,5-HAT process to derive heteroarylated amides (30) under photoredox conditions (Scheme 13). [54] The proposed mechanism involves the formation of amidyl radical from hydroxamide via single-electron reduction assisted by photoexcited 3CzClIPN* along with the generation of carboxylate anion and 3CzClIPN + . 1,5-HAT from carbon to nitrogen then generates a carbon-centered radical from carbon to nitrogen which subsequently delivers the desired product upon the loss of hydrogen atom in the presence of a base.…”
Section: Intramolecular Hat (15 Hat) Approachesmentioning
confidence: 99%
“…63 Late-stage modification of amide-based bioactive molecules opens an efficient arena for drug screening. Inspired by the pioneering Hofmann-Löffler-Freytag (HLF) reaction that enables pyrrolidine formation via remote C(sp 3 )-H functionalization of aliphatic amines (Scheme 9), 3 recently many research groups, for example, Li, 64,65 Cook, 66 Muñiz, 67 Studer, 68,69 Yu, 70,71 Zhu, 72,73 Nagib, 74 Roizen, 75 Wang, 76 Leonori, 77 Hong, 78 Liu, 79 and Yang 80 et al, have made new breakthroughs in amidyl radical-mediated remote C(sp 3 )-H functionalization. Notably, Liu et al 81 achieved the copper-catalyzed regio-and enantio-selective Sonogashira-type oxidative cross-coupling of C(sp 3 )-H bonds with alkynes by using N-fluoroamides as amidyl radical precursors.…”
Section: Traditional Pathwaymentioning
confidence: 99%