Electrophotocatalysis with a Trisaminocyclopropenium Radical Dication
Abstract
Abstract 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.
- Authors:
-
- Department of Chemistry and Chemical Biology Cornell University Ithaca NY 14853 USA
- Department of Chemistry Columbia University New York NY 10027 USA
- Department of Chemistry and Chemical Biology Cornell University Ithaca NY 14853 USA, Department of Chemistry Columbia University New York NY 10027 USA
- Publication Date:
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1546094
- Resource Type:
- Publisher's Accepted Manuscript
- Journal Name:
- Angewandte Chemie
- Additional Journal Information:
- Journal Name: Angewandte Chemie Journal Volume: 131 Journal Issue: 38; Journal ID: ISSN 0044-8249
- Publisher:
- Wiley Blackwell (John Wiley & Sons)
- Country of Publication:
- Germany
- Language:
- English
Citation Formats
Huang, He, Strater, Zack M., Rauch, Michael, Shee, James, Sisto, Thomas J., Nuckolls, Colin, and Lambert, Tristan H. Electrophotocatalysis with a Trisaminocyclopropenium Radical Dication. Germany: N. p., 2019.
Web. doi:10.1002/ange.201906381.
Huang, He, Strater, Zack M., Rauch, Michael, Shee, James, Sisto, Thomas J., Nuckolls, Colin, & Lambert, Tristan H. Electrophotocatalysis with a Trisaminocyclopropenium Radical Dication. Germany. https://doi.org/10.1002/ange.201906381
Huang, He, Strater, Zack M., Rauch, Michael, Shee, James, Sisto, Thomas J., Nuckolls, Colin, and Lambert, Tristan H. Fri .
"Electrophotocatalysis with a Trisaminocyclopropenium Radical Dication". Germany. https://doi.org/10.1002/ange.201906381.
@article{osti_1546094,
title = {Electrophotocatalysis with a Trisaminocyclopropenium Radical Dication},
author = {Huang, He and Strater, Zack M. and Rauch, Michael and Shee, James and Sisto, Thomas J. and Nuckolls, Colin and Lambert, Tristan H.},
abstractNote = {Abstract 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.},
doi = {10.1002/ange.201906381},
journal = {Angewandte Chemie},
number = 38,
volume = 131,
place = {Germany},
year = {Fri Aug 02 00:00:00 EDT 2019},
month = {Fri Aug 02 00:00:00 EDT 2019}
}
https://doi.org/10.1002/ange.201906381
Works referenced in this record:
Solar Synthesis: Prospects in Visible Light Photocatalysis
journal, February 2014
- Schultz, D. M.; Yoon, T. P.
- Science, Vol. 343, Issue 6174
Phenothiazine Radical Cation Excited States as Super-oxidants for Energy-Demanding Reactions
journal, March 2018
- Christensen, Joseph A.; Phelan, Brian T.; Chaudhuri, Subhajyoti
- Journal of the American Chemical Society, Vol. 140, Issue 15
Organic Photoredox Catalysis
journal, June 2016
- Romero, Nathan A.; Nicewicz, David A.
- Chemical Reviews, Vol. 116, Issue 17
Accurate Oxidation Potentials of Benzene and Biphenyl Derivatives via Electron-Transfer Equilibria and Transient Kinetics
journal, August 2009
- Merkel, Paul B.; Luo, Pu; Dinnocenzo, Joseph P.
- The Journal of Organic Chemistry, Vol. 74, Issue 15
Photoelectrochemical C−H Alkylation of Heteroarenes with Organotrifluoroborates
journal, February 2019
- Yan, Hong; Hou, Zhong-Wei; Xu, Hai-Chao
- Angewandte Chemie International Edition, Vol. 58, Issue 14
Catalysis of Radical Reactions: A Radical Chemistry Perspective
journal, October 2015
- Studer, Armido; Curran, Dennis P.
- Angewandte Chemie International Edition, Vol. 55, Issue 1
Tris (dimethylamino)-cyclopropenium radical dication
journal, January 1971
- Gerson, F.; Plattner, G.; Yoshida, Z.
- Molecular Physics, Vol. 21, Issue 6
Direct Oxygenation of Benzene to Phenol Using Quinolinium Ions as Homogeneous Photocatalysts
journal, August 2011
- Ohkubo, Kei; Kobayashi, Takaki; Fukuzumi, Shunichi
- Angewandte Chemie, Vol. 123, Issue 37
Phototochemistry of cation radicals in solution; photoinduced electron-transfer reactions between alcholos and the N,N,N′,N′,-tetraphenyl-p-phenylenediamine cation radical
journal, January 1982
- Moutet, Jean-Claude; Reverdy, Gilbert
- J. Chem. Soc., Chem. Commun., Vol. 0, Issue 12
Merging Photochemistry with Electrochemistry: Functional‐Group Tolerant Electrochemical Amination of C(sp 3 )−H Bonds
journal, February 2019
- Wang, Fei; Stahl, Shannon S.
- Angewandte Chemie, Vol. 131, Issue 19
Visible-light excitation of iminium ions enables the enantioselective catalytic β-alkylation of enals
journal, March 2017
- Silvi, Mattia; Verrier, Charlie; Rey, Yannick P.
- Nature Chemistry, Vol. 9, Issue 9
Redox catalysis in organic electrosynthesis: basic principles and recent developments
journal, January 2014
- Francke, Robert; Little, R. Daniel
- Chemical Society Reviews, Vol. 43, Issue 8
Modern Strategies in Electroorganic Synthesis
journal, July 2008
- Yoshida, Jun-ichi; Kataoka, Kazuhide; Horcajada, Roberto
- Chemical Reviews, Vol. 108, Issue 7
SOMO–HOMO Level Inversion in Biologically Important Radicals
journal, December 2017
- Kumar, Anil; Sevilla, Michael D.
- The Journal of Physical Chemistry B, Vol. 122, Issue 1
Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance
journal, October 2017
- Yan, Ming; Kawamata, Yu; Baran, Phil S.
- Chemical Reviews, Vol. 117, Issue 21
Merging Photochemistry with Electrochemistry: Functional-Group Tolerant Electrochemical Amination of C(sp 3 )−H Bonds
journal, March 2019
- Wang, Fei; Stahl, Shannon S.
- Angewandte Chemie International Edition, Vol. 58, Issue 19
Synthesis and reactions of porphine-type metal complexes. 15. Carbon-carbon bond formation by light assisted B12-catalysis. Nucleophilic acylation of Michael olefins
journal, November 1983
- Scheffold, Rolf; Orlinski, Ryszard
- Journal of the American Chemical Society, Vol. 105, Issue 24
Visible-Light-Induced Oxygenation of Benzene by the Triplet Excited State of 2,3-Dichloro-5,6-dicyano- p -benzoquinone
journal, March 2013
- Ohkubo, Kei; Fujimoto, Atsushi; Fukuzumi, Shunichi
- Journal of the American Chemical Society, Vol. 135, Issue 14
Studies Leading to the Development of a Single-Electron Transfer (SET) Photochemical Strategy for Syntheses of Macrocyclic Polyethers, Polythioethers, and Polyamides
journal, March 2011
- Cho, Dae Won; Yoon, Ung Chan; Mariano, Patrick S.
- Accounts of Chemical Research, Vol. 44, Issue 3
Cyclopropenium Salts as Cyclable, High-Potential Catholytes in Nonaqueous Media
journal, November 2016
- Sevov, Christo S.; Samaroo, Sharmila K.; Sanford, Melanie S.
- Advanced Energy Materials, Vol. 7, Issue 5
Katalyse von Radikalreaktionen: Konzepte aus Sicht der Radikalchemie
journal, October 2015
- Studer, Armido; Curran, Dennis P.
- Angewandte Chemie, Vol. 128, Issue 1
Synthetic Applications of Anodic Electrochemistry
journal, December 2000
- Moeller, Kevin D.
- Tetrahedron, Vol. 56, Issue 49
Photoelectrocatalytic arene C–H amination
journal, February 2019
- Zhang, Lei; Liardet, Laurent; Luo, Jingshan
- Nature Catalysis, Vol. 2, Issue 4
Stable radical dications
journal, January 1975
- Weiss, Robert; Schloter, Klaus
- Tetrahedron Letters, Vol. 16, Issue 40
Site-selective arene C-H amination via photoredox catalysis
journal, September 2015
- Romero, N. A.; Margrey, K. A.; Tay, N. E.
- Science, Vol. 349, Issue 6254
Direct Oxygenation of Benzene to Phenol Using Quinolinium Ions as Homogeneous Photocatalysts
journal, August 2011
- Ohkubo, Kei; Kobayashi, Takaki; Fukuzumi, Shunichi
- Angewandte Chemie International Edition, Vol. 50, Issue 37
Photoelectrochemical C−H Alkylation of Heteroarenes with Organotrifluoroborates
journal, January 2019
- Yan, Hong; Hou, Zhong‐Wei; Xu, Hai‐Chao
- Angewandte Chemie, Vol. 131, Issue 14
Photo-induced oxidant-free oxidative C–H/N–H cross-coupling between arenes and azoles
journal, February 2017
- Niu, Linbin; Yi, Hong; Wang, Shengchun
- Nature Communications, Vol. 8, Issue 1
Electrochemistry of heterosubstituted cyclopropenyl cations
journal, February 1976
- Johnson, Richard W.
- Tetrahedron Letters, Vol. 17, Issue 8
Photoredox Catalysis in Organic Chemistry
journal, June 2016
- Shaw, Megan H.; Twilton, Jack; MacMillan, David W. C.
- The Journal of Organic Chemistry, Vol. 81, Issue 16
Visible light photoredox catalysis: applications in organic synthesis
journal, January 2011
- Narayanam, Jagan M. R.; Stephenson, Corey R. J.
- Chem. Soc. Rev., Vol. 40, Issue 1
Aminocyclopropenium Ions: Synthesis, Properties, and Applications
journal, August 2013
- Bandar, Jeffrey; Lambert, Tristan
- Synthesis, Vol. 45, Issue 18