The DOI matches its Crossref record; 31 of the 31 references it cites were found in a registry or an index.
Rhodium-Catalyzed C–H Activation of Phenacyl Ammonium Salts Assisted by an Oxidizing C–N Bond: A Combination of Experimental and Theoretical Studies
Abstract
Rh(III)-catalyzed C-H activation assisted by an oxidizing directing group has evolved to a mild and redox-economic strategy for the construction of heterocycles. Despite the success, these coupling systems are currently limited to cleavage of an oxidizing N-O or N-N bond. Cleavage of an oxidizing C-N bond, which allows for complementary carbocycle synthesis, is unprecedented. In this article, α-ammonium acetophenones with an oxidizing C-N bond have been designed as substrates for Rh(III)-catalyzed C-H activation under redox-neutral conditions. The coupling with α-diazo esters afforded benzocyclopentanones, and the coupling with unactivated alkenes such as styrenes and aliphatic olefins gave ortho-olefinated acetophenoes. In both systems the reactions proceeded with a broad scope, high efficiency, and functional group tolerance. Moreover, efficient one-pot coupling of diazo esters has been realized starting from α-bromoacetophenones and triethylamine. The reaction mechanism for the coupling with diazo esters has been studied by a combination of experimental and theoretical methods. In particular, three distinct mechanistic pathways have been scrutinized by DFT studies, which revealed that the C-H activation occurs via a C-bound enolate-assisted concerted metalation-deprotonation mechanism and is rate-limiting. In subsequent C-C formation steps, the lowest energy pathway involves two rhodium carbene species as key intermediates.
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Metadata
- Authors
- Yu, S., Liu, S., Lan, Y., Wan, B., & Li, X.
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Published
- 2015-01-21
- Volume
- 137
- Issue
- 4
- Pages
- 1623-1631
- ISSN
- 0002-7863 (ISSN-L)
- 1520-5126
- OpenAlex
- W2326552731
- Cited by
- 331
- References
- 31
- FWCI
- 30.72
- Type
- journal article
- Language
- en
- Open access
- closed
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