Electrophotocatalysis with a Trisaminocyclopropenium Radical Dication.
C−H functionalization
Electrophotocatalysis
oxidation
radical dication
trisaminocyclopropenium ion
Journal
Angewandte Chemie (International ed. in English)
ISSN: 1521-3773
Titre abrégé: Angew Chem Int Ed Engl
Pays: Germany
ID NLM: 0370543
Informations de publication
Date de publication:
16 09 2019
16 09 2019
Historique:
received:
22
05
2019
revised:
18
06
2019
pubmed:
16
7
2019
medline:
18
9
2020
entrez:
16
7
2019
Statut:
ppublish
Résumé
Visible-light photocatalysis and electrocatalysis are two powerful strategies for the promotion of chemical reactions. Here, these two modalities are combined in an electrophotocatalytic oxidation platform. This chemistry employs a trisaminocyclopropenium (TAC) ion catalyst, which is electrochemically oxidized to form a cyclopropenium radical dication intermediate. The radical dication undergoes photoexcitation with visible light to produce an excited-state species with oxidizing power (3.33 V vs. SCE) sufficient to oxidize benzene and halogenated benzenes via single-electron transfer (SET), resulting in C-H/N-H coupling with azoles. A rationale for the strongly oxidizing behavior of the photoexcited species is provided, while the stability of the catalyst is rationalized by a particular conformation of the cis-2,6-dimethylpiperidine moieties.
Identifiants
pubmed: 31306561
doi: 10.1002/anie.201906381
pmc: PMC7168342
mid: NIHMS1578921
doi:
Substances chimiques
Free Radicals
0
Types de publication
Journal Article
Research Support, N.I.H., Extramural
Research Support, U.S. Gov't, Non-P.H.S.
Langues
eng
Sous-ensembles de citation
IM
Pagination
13318-13322Subventions
Organisme : NIGMS NIH HHS
ID : R35 GM127135
Pays : United States
Organisme : National Science Foundation
ID : DGE-16-44869
Pays : International
Organisme : Basic Energy Sciences
ID : DE-SC001944
Pays : International
Organisme : National Science Foundation
ID : CHE-0619638
Pays : International
Informations de copyright
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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