Nickel catalysed SET-induced oxygenation of (aryl)(N-heteroaryl)methanes with molecular oxygen

Abstract

Nickel catalyzed C–H oxygenation is a fundamentally important, but much less studied transformation. Herein, we report a nickel based catalyst that, in combination with catalytic DDQ, promotes the oxygenation of (aryl)(N-heteroaryl)methanes with molecular oxygen under neutral conditions. The strategy involves SET-induced formation of C-centered radicals giving access to (aryl)(N-heteroaryl)ketones and is extended to arylbenzyl ketones. The current approach has been successfully applied for the synthesis of an intermediate of AMG 579, an investigational drug candidate. A slightly modified catalyst system enables the synthesis of benzoxazinones directly starting from (aryl)(N-heteroaryl)methanes.