Denitrogenative N-O Coupling of Benzyl Azides with N-Hydroxyphthalimide Mediated by Cerium(IV) Ammonium Nitrate as an
Stanislav A Paveliev1, Andrey A Dvoretskiy1, Oleg O Segida1
1N. D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences, 47 Leninsky prosp., Moscow 119991, Russian Federation.
Abstract:
An intermolecular N-O coupling process between iminyl radicals derived from benzyl azides and phthalimide-N-oxyl radicals, leading to the O-phthalimide oximes with a rare N-O-N fragment, was discovered. The present work reveals an unusual reactivity of organic azides: they are introduced into the denitrogenative generation of N-centered iminyl radicals via hydrogen atom abstraction from the α-position of the azide group. Moreover, the method exploits the dual reactivity of the phthalimide-N-oxyl radical, which acts both as a mediator of hydrogen atom abstraction and an interceptor of intermediate iminyl radicals.
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