Show simple item record

dc.contributor.authorMaity, Bholanath
dc.contributor.authorZhu, Chen
dc.contributor.authorYue, Huifeng
dc.contributor.authorHuang, Long
dc.contributor.authorHarb, Moussab
dc.contributor.authorMinenkov, Yury
dc.contributor.authorRueping, Magnus
dc.contributor.authorCavallo, Luigi
dc.date.accessioned2020-09-13T09:45:02Z
dc.date.available2020-09-13T09:45:02Z
dc.date.issued2020-09-09
dc.identifier.citationMaity, B., Zhu, C., Yue, H., Huang, L., Harb, M., Minenkov, Y., … Cavallo, L. (2020). Mechanistic Insight into the Photoredox-Nickel-HAT Triple Catalyzed Arylation and Alkylation of α-Amino Csp3–H Bonds. Journal of the American Chemical Society. doi:10.1021/jacs.0c05010
dc.identifier.issn0002-7863
dc.identifier.issn1520-5126
dc.identifier.doi10.1021/jacs.0c05010
dc.identifier.urihttp://hdl.handle.net/10754/665080
dc.description.abstractWe report here a comprehensive computational analysis of the mechanisms of the photoredox-nickel-HAT (HAT: hydrogen atom transfer) catalyzed arylation and alkylation of α-amino Csp3–H bonds developed by MacMillan and coworkers. Different alternatives for the three catalytic cycles were tested to identify unambiguously the operative reaction mechanism. Our analysis indicated that the IrIII photoredox catalyst, upon irradiation with visible light, can be either reduced or oxidized by the HAT and nickel catalysts, respectively, indicating that both reductive and oxidative quenching catalytic cycles can be operative, although the reductive cycle is favored. Our analysis of the HAT cycle indicated that activation of a α-amino Csp3‒H bond of the substrate is facile and selective relative to activation of a β-amino Csp3‒H bond. Finally, our analysis of the nickel cycle indicated that both arylation and alkylation of α-amino Csp3–H bonds occurs via the sequence of nickel oxidation states NiI-NiII-NiI-NiIII, and of elementary steps: radical addition-SET-oxidative addition-reductive elimination.
dc.description.sponsorshipWe acknowledge King Abdullah University of Science and Technology (KAUST) for support and the KAUST Supercomputing Laboratory for providing computational resources of the supercomputer Shaheen II.
dc.publisherAmerican Chemical Society (ACS)
dc.relation.urlhttps://pubs.acs.org/doi/10.1021/jacs.0c05010
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/jacs.0c05010.
dc.titleMechanistic Insight into the Photoredox-Nickel-HAT Triple Catalyzed Arylation and Alkylation of α-Amino Csp3–H Bonds
dc.typeArticle
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.contributor.departmentChemical Science Program
dc.identifier.journalJournal of the American Chemical Society
dc.rights.embargodate2021-09-09
dc.eprint.versionPost-print
dc.contributor.institutionInstitute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany.
dc.contributor.institutionN. N. Semenov Federal Research Center for Chemical Physics, Kosygina Street 4, 119991 Moscow, Russia.
kaust.personMaity, Bholanath
kaust.personZhu, Chen
kaust.personYue, Huifeng
kaust.personHarb, Moussab
kaust.personRueping, Magnus
kaust.personCavallo, Luigi
refterms.dateFOA2020-09-14T05:42:37Z
kaust.acknowledged.supportUnitKAUST Supercomputing Laboratory
kaust.acknowledged.supportUnitsupercomputer Shaheen II
dc.date.published-online2020-09-09
dc.date.published-print2020-10-07


Files in this item

Thumbnail
Name:
Revised_Csp3-H_Manuscript_R3-2020-08-16.pdf
Size:
1.027Mb
Format:
PDF
Description:
Accepted manuscript

This item appears in the following Collection(s)

Show simple item record