Peroxidation and Skeletal Rearrangement for the Synthesis of Dioxole‐2‐Carboxamide Derivatives under Continuous‐Flow Conditions

Abstract

Herein, we report peroxidative dearomatisation of 2‐naphthol and C‐H peroxidation of 3‐arylbenzofuran‐2‐ones up to 94% yield under catalyst‐free conditions using continuous flow module. Besides, an approach for the synthesis of N‐substituted‐2‐phenylbenzo[d][1,3]dioxole‐2‐carboxamide has been achieved via the skeletal rearrangement of peroxybenzofuranone using amines in the absence of catalyst under continuous flow. The mechanistic study suggests that this peroxidation reaction proceeds via free radical formation under thermolytic conditions.

Continuous flow synthesis enabling reaction discovery

“…Examples include a recently published synthesis of substituted benzo[d][1,3]dioxoles from peroxides and amides as reported by Gnanaprakasam and coworkers. 62 Similarly, the Kirschning group combined ow processing with inductive heating methods leading to the oxidative conversion of cyclic ketones into ring-expanded esters as well as hydrocarbons in the presence of H 2 O 2 /HNO 3 . 63 The Jamison group reported a ow-based access to diimide from N,O-bistri-uoroacetyl hydroxylamine and free hydroxylamine to affect the saturation of various alkenes at elevated temperatures in ow mode.…”

“…Examples include a recently published synthesis of substituted benzo[ d ][1,3]dioxoles from peroxides and amides as reported by Gnanaprakasam and coworkers. 62 …”