Mechanistic insights into copper-catalyzed aerobic oxidative coupling of N–N bonds
Abstract
Catalytic N–N coupling is a valuable transformation for chemical synthesis and energy conversion. Here, mechanistic studies are presented for two related copper-catalyzed oxidative aerobic N–N coupling reactions, one involving the synthesis of a pharmaceutically relevant triazole and the other relevant to the oxidative conversion of ammonia to hydrazine. Analysis of catalytic and stoichiometric N–N coupling reactions support an “oxidase”-type catalytic mechanism with two redox half-reactions: (1) aerobic oxidation of a CuI catalyst and (2) CuII-promoted N–N coupling. Both reactions feature turnover-limiting oxidation of CuI by O2, and this step is inhibited by the N–H substrate(s). The results highlight the unexpected facility of the N–N coupling step and establish a foundation for development of improved catalysts for these transformations.
- Authors:
-
- Department of Chemistry, University of Wisconsin–Madison, Madison, USA
- Small Molecule Design and Development, Lilly Research Laboratories, Eli Lilly and Company, Indianapolis, USA
- Publication Date:
- Research Org.:
- Univ. of Wisconsin, Madison, WI (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1579758
- Alternate Identifier(s):
- OSTI ID: 1800250
- Grant/Contract Number:
- FG02-05ER15690
- Resource Type:
- Published Article
- Journal Name:
- Chemical Science
- Additional Journal Information:
- Journal Name: Chemical Science Journal Volume: 11 Journal Issue: 4; Journal ID: ISSN 2041-6520
- Publisher:
- Royal Society of Chemistry (RSC)
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Ryan, Michael C., Kim, Yeon Jung, Gerken, James B., Wang, Fei, Aristov, Michael M., Martinelli, Joseph R., and Stahl, Shannon S. Mechanistic insights into copper-catalyzed aerobic oxidative coupling of N–N bonds. United Kingdom: N. p., 2020.
Web. doi:10.1039/C9SC04305E.
Ryan, Michael C., Kim, Yeon Jung, Gerken, James B., Wang, Fei, Aristov, Michael M., Martinelli, Joseph R., & Stahl, Shannon S. Mechanistic insights into copper-catalyzed aerobic oxidative coupling of N–N bonds. United Kingdom. https://doi.org/10.1039/C9SC04305E
Ryan, Michael C., Kim, Yeon Jung, Gerken, James B., Wang, Fei, Aristov, Michael M., Martinelli, Joseph R., and Stahl, Shannon S. Wed .
"Mechanistic insights into copper-catalyzed aerobic oxidative coupling of N–N bonds". United Kingdom. https://doi.org/10.1039/C9SC04305E.
@article{osti_1579758,
title = {Mechanistic insights into copper-catalyzed aerobic oxidative coupling of N–N bonds},
author = {Ryan, Michael C. and Kim, Yeon Jung and Gerken, James B. and Wang, Fei and Aristov, Michael M. and Martinelli, Joseph R. and Stahl, Shannon S.},
abstractNote = {Catalytic N–N coupling is a valuable transformation for chemical synthesis and energy conversion. Here, mechanistic studies are presented for two related copper-catalyzed oxidative aerobic N–N coupling reactions, one involving the synthesis of a pharmaceutically relevant triazole and the other relevant to the oxidative conversion of ammonia to hydrazine. Analysis of catalytic and stoichiometric N–N coupling reactions support an “oxidase”-type catalytic mechanism with two redox half-reactions: (1) aerobic oxidation of a CuI catalyst and (2) CuII-promoted N–N coupling. Both reactions feature turnover-limiting oxidation of CuI by O2, and this step is inhibited by the N–H substrate(s). The results highlight the unexpected facility of the N–N coupling step and establish a foundation for development of improved catalysts for these transformations.},
doi = {10.1039/C9SC04305E},
journal = {Chemical Science},
number = 4,
volume = 11,
place = {United Kingdom},
year = {Wed Jan 29 00:00:00 EST 2020},
month = {Wed Jan 29 00:00:00 EST 2020}
}
https://doi.org/10.1039/C9SC04305E
Web of Science
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