- Mechanism-Driven Approach To Develop a Mild and Versatile C?H Amidation through IrIII Catalysis
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Described herein is a mechanism-based approach to develop a versatile C?H amidation protocol under IrIII catalysis. Reaction kinetics of a key C?N coupling step with acyl azide and 1,4,2-dioxazol-5-one led us to conclude that dioxazolones are much more efficient in mediating the formation of a carbon?nitrogen bond from an iridacyclic intermediate. Computational analysis revealed that the origin of higher reactivity is asynchronous decarboxylation motion, which may facilitate the formation of Ir-imido species. Importantly, stoichiometric reactivity was successfully translated into catalytic activity with a broad range of substrates (18 different types), many of which are regarded as challenging to functionalize. Application of the new method enables late-stage functionalization of drug molecules.
- Hwang, Yeongyu,Park, Yoonsu,Chang, Sukbok
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- Process for the preparation of arylamide and enamide derivatives using organic axide and iridium catalyst
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The present invention refers to arene (arenes) organic compound (alkenes) alkene or flouride iridium compounds and middle portion of a fixing plate under catalyst (iridium complex) carbon-hydrogen bonds, amination directly into carbon-nitrogen bond being manufactured with low ratio of carbon layer on the novel manufacturing method.
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Paragraph 0064-0066
(2016/12/16)
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- Ir(III)-catalyzed mild C-H amidation of arenes and alkenes: An efficient usage of acyl azides as the nitrogen source
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Reported herein is the development of the Ir(III)-catalyzed direct C-H amidation of arenes and alkenes using acyl azides as the nitrogen source. This procedure utilizes an in situ generated cationic half-sandwich iridium complex as a catalyst. The reaction takes place under very mild conditions, and a broad range of sp2 C-H bonds of chelate group-containing arenes and olefins are smoothly amidated with acyl azides without the intervention of the Curtius rearrangement. Significantly, a wide range of reactants of aryl-, aliphatic-, and olefinic acyl azides were all efficiently amidated with high functional group tolerance. Using the developed approach, Z-enamides were readily accessed with a complete control of regio- and stereoselectivity. The developed direct amidation proceeds in the absence of external oxidants and releases molecular nitrogen as a single byproduct, thus offering an environmentally benign process with wide potential applications in organic synthesis and medicinal chemistry.
- Ryu, Jaeyune,Kwak, Jaesung,Shin, Kwangmin,Lee, Donggun,Chang, Sukbok
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p. 12861 - 12868
(2013/09/23)
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