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 Studies on the Rh(III)-Mediated Amido Transfer Process Leading to Robust C-H Amination with a New Type of Amidating Reagent
- Yoonsu Park; Kyung Tae Park; Jeung Gon Kim; Sukbok Chang
- JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.137, no.13, pp.4534 - 4542
- AMER CHEMICAL SOC
- 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. © 2015 American Chemical Society
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