Visible-Light-Mediated Synthesis of β-Chloro Ketones from Aryl Cyclopropanes

Abstract

We report the visible-light-mediated synthesis of β-chloro ketones from aryl cyclopropanes, oxygen, hydrochloric acid, and nitric acid. The operationally simple and catalyst-free method uses cheap standard laboratory reagents and displays broad functional-group tolerance. Moreover, scale up of the reaction and late-stage functionalization of bioactive compounds is possible, providing the opportunity to utilize the cyclopropane ring as a masked β-chloro ketone in a reaction sequence. We propose a light-driven radical chain reaction initiated by the reaction of diluted hydrochloric and nitric acid to produce small quantities of molecular chlorine. The mechanistic hypothesis is supported by ¹⁸ O labelling and UV/Vis experiments, cyclovoltammetry, and several control reactions.

Keywords: aryl cyclopropane; late-stage modification; photochemistry; radical chain reactions; β-chloro ketones.