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Photochemical C(sp2)−H Pyridination via Arene–Pyridinium Electron Donor–Acceptor Complexes

dc.contributor.authorLasky, Matthew R.
dc.contributor.authorSalvador, Tolani K.
dc.contributor.authorMukhopadhyay, Sukrit
dc.contributor.authorRemy, Matthew S.
dc.contributor.authorVaid, Thomas P.
dc.contributor.authorSanford, Melanie S.
dc.date.accessioned2022-12-05T16:39:21Z
dc.date.available2023-12-05 11:39:16en
dc.date.available2022-12-05T16:39:21Z
dc.date.issued2022-11-14
dc.identifier.citationLasky, Matthew R.; Salvador, Tolani K.; Mukhopadhyay, Sukrit; Remy, Matthew S.; Vaid, Thomas P.; Sanford, Melanie S. (2022). "Photochemical C(sp2)−H Pyridination via Arene–Pyridinium Electron Donor–Acceptor Complexes." Angewandte Chemie 134(46): n/a-n/a.
dc.identifier.issn0044-8249
dc.identifier.issn1521-3757
dc.identifier.urihttps://hdl.handle.net/2027.42/175192
dc.description.abstractThis report describes the development of a photochemical method for C(sp2)−H pyridination that leverages the photoexcitation of electron donor–acceptor (EDA) complexes. Experimental and DFT studies show that black light (λmax≈350 nm) irradiation of solutions of protonated pyridines (acceptors) and aromatic C−H substrates (donors) results in single electron transfer to form aryl radical cation intermediates that can be trapped with pyridine nucleophiles under aerobic conditions. With some modification of the reaction conditions, this EDA activation mode is also effective for promoting the oxidatively triggered SNAr pyridination of aryl halides. Overall, this report represents an inexpensive and atom-economical approach to photochemical pyridination reactions that eliminates the requirement of an exogenous photocatalyst.We leverage the photoexcitation of arene–pyridinium electron donor–acceptor (EDA) complexes to achieve C(sp2)−H pyridination. Black light irradiation of the simple combination of arene substrate, pyridine, acid (to generate a pyridinium acceptor in situ), and O2 (terminal oxidant) affords N-arylpyridinium products. This transformation proceeds without an exogenous photocatalyst, complementing prior photochemical C(sp2)−H amination methods.
dc.publisherWiley Periodicals, Inc.
dc.subject.otherPhotochemistry
dc.subject.otherReaction Mechanisms
dc.subject.otherC−H Functionalization
dc.subject.otherN-Heterocycles
dc.subject.otherRadical Intermediates
dc.titlePhotochemical C(sp2)−H Pyridination via Arene–Pyridinium Electron Donor–Acceptor Complexes
dc.typeArticle
dc.rights.robotsIndexNoFollow
dc.subject.hlbsecondlevelMaterials Science and Engineering
dc.subject.hlbsecondlevelChemistry
dc.subject.hlbsecondlevelChemical Engineering
dc.subject.hlbtoplevelScience
dc.subject.hlbtoplevelEngineering
dc.description.peerreviewedPeer Reviewed
dc.description.bitstreamurlhttp://deepblue.lib.umich.edu/bitstream/2027.42/175192/1/ange202208741_am.pdf
dc.description.bitstreamurlhttp://deepblue.lib.umich.edu/bitstream/2027.42/175192/2/ange202208741-sup-0001-misc_information.pdf
dc.description.bitstreamurlhttp://deepblue.lib.umich.edu/bitstream/2027.42/175192/3/ange202208741.pdf
dc.identifier.doi10.1002/ange.202208741
dc.identifier.sourceAngewandte Chemie
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dc.working.doiNOen
dc.owningcollnameInterdisciplinary and Peer-Reviewed


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