Mechanistic Studies on the Rh(III)-Mediated Amido Transfer Process Leading to Robust C-H Amination with a New Type of Amidating Reagent

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Mechanistic investigations on the Cp*Rh(III)-catalyzed direct C-H amination reaction led us to reveal the new utility of 1,4,2-dioxazol-5-one and its derivatives as highly efficient amino sources. Stepwise analysis on the C-N bond-forming process showed that competitive binding of rhodium metal center to amidating reagent or substrate is closely related to the reaction efficiency. In this line, 1,4,2-dioxazol-5-ones were observed to have a strong affinity to the cationic Rh(III) giving rise to dramatically improved amidation efficiency when compared to azides. Kinetics and computational studies suggested that the high amidating reactivity of 1,4,2-dioxazol-5-one can also be attributed to the low activation energy of an imido-insertion process in addition to the high coordination ability. While the characterization of a cationic Cp*Rh(III) complex bearing an amidating reagent was achieved, its facile conversion to an amido-inserted rhodacycle allowed for a clear picture on the C-H amidation process. The newly developed amidating reagent of 1,4,2-dioxazol-5-ones was applicable to a broad range of substrates with high functional group tolerance, releasing carbon dioxide as a single byproduct. Additional attractive features of this amino source, such as they are more convenient to prepare, store, and use when compared to the corresponding azides, take a step closer toward an ideal C-H amination protocol.
Publisher
AMER CHEMICAL SOC
Issue Date
2015-04
Language
English
Article Type
Article
Keywords

N BOND FORMATION; CARBON-NITROGEN BONDS; SULFONYL AZIDES; INTERMOLECULAR AMIDATION; COUPLING REACTIONS; FORMING REACTIONS; AROMATIC KETONES; NATURAL-PRODUCTS; SYNTHETIC ROUTE; ATOM-TRANSFER

Citation

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.137, no.13, pp.4534 - 4542

ISSN
0002-7863
DOI
10.1021/jacs.5b01324
URI
http://hdl.handle.net/10203/200980
Appears in Collection
CH-Journal Papers(저널논문)
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