Baeyer–Villiger oxidation under Payne epoxidation conditions

Abstract

A novel method for the Baeyer–Villiger oxidation of ketones has been developed and optimized. The transformation involves a transition metal-free activation of hydrogen peroxide under Payne epoxidation conditions. Reaction of a ketone with hydrogen peroxide in the presence of a nitrile under mildly basic reaction conditions leads to the corresponding ester. The transformation has been successfully applied to a range of ketones in moderate to excellent yields (30–91 and good to excellent regioselectivities (7:1 to 20:1)

Rearrangements of organic peroxides and related processes

“…The esters 86 were synthesized by the reaction of ketones 85 with H 2 O 2 and benzonitrile under basic reaction conditions (KHCO 3 ) with the intermediate generation of peroxyimidic acids. This oxidation can be successfully applied to alkyl-containing ketones to give the target products in yields of 30–91% and good regioselectivity 7:1 to 20:1 ( Scheme 28 ) [ 261 ].…”

Urea‐2,2‐dihydroperoxypropane as a Novel and High Oxygen Content Alternative to Dihydroperoxypropane in Several Oxidation Reactions

“…The Bayer‐villiger oxidation has become a valuable transformation in synthesis,, since its discovery in 1899, 21 due to its versatile applications in industrial organic synthesis, pharmacy, medicine, cosmetic industry, organo chemistry and polymer manufacturing . m‐ chloroperbenzoic acid, a commercially available reagent, has been widely used in oxidative reactions.…”

Purified mCPBA, a Useful Reagent for the Oxidation of Aldehydes

“…Although in their original work Baeyer and Villiger used Caro's acid (H 2 SO 5 ) to oxidize menthone towards the corresponding lactone, a wide range of peracids are generally used nowadays, for which the oxidation power of the peracids correlates with the acidity of the corresponding carboxylic acid . Weaker oxidation reagents, such as H 2 O 2 do not undergo BV oxidation but require “activation“, either by transition metal complexes, or nitriles, which generate imido peracids in situ . Especially the oxidation of ketones became a standard protocol in organic synthesis and finds widespread application in industry .…”