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Aryl–Cu(III) Nitrene錯体によるC-H Abstraction

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Copper nitrenes are of interest as intermediates in the catalytic aziridination of olefins and the amination of C-H bonds.
 
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Abstract
 
High-valent terminal copper–nitrene species have been postulated as key intermediates in copper-catalyzed aziridination and amination reactions.
 
The high reactivity of these intermediates has prevented their characterization for decades, thereby making the mechanisms ambiguous.
 
Very recently, the Lewis acid adduct of a copper–nitrene intermediate was trapped at −90 °C and shown to be active in various oxidation reactions.
 
Herein, we describe for the first time the synthesis and spectroscopic characterization of a terminal copper(II)–nitrene radical species that is stable at room temperature in the absence of any Lewis acid.
 
The azide derivative of a triazamacrocyclic ligand that had previously been utilized in the stabilization of aryl–CuIII intermediates was employed as an ancillary ligand in the study.
 
The terminal copper(II)–nitrene radical species is able to transfer a nitrene moiety to phosphines and abstract a hydrogen atom from weak C−H bonds, leading to the formation of oxidized products in modest yields.
 
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