Copper-catalyzed aerobic nitrogen-migration cyanation and oxygenation of unsaturated ketoximes via the CC bond cleavage: facile access to 4-oxobutanenitriles?

Organic Chemistry Frontiers Pub Date: 2022-10-29 DOI: 10.1039/D2QO01553F

Abstract

A new copper-catalyzed aerobic synthesis of 4-oxobutanenitriles by the nitrogen-migration cyanation and oxygenation of γ,δ-unsaturated ketoximes at room temperature is developed. By means of a copper(0) powder catalyst, the nitrogen-migration cyanation and oxygenation of unsaturated ketoximes with O2via a radical intramolecular 5-exo-trig cyclization, C[double bond, length as m-dash]C double bond cleavage and ring-opening process efficiently execute to assemble 4-oxobutanenitriles. Mechanistic studies indicate that these processes include radicals initiating the reaction from the oxime side and the superoxide radical formation.

Graphical abstract: Copper-catalyzed aerobic nitrogen-migration cyanation and oxygenation of unsaturated ketoximes via the C [[double bond, length as m-dash]] C bond cleavage: facile access to 4-oxobutanenitriles
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