Oxidative α-acyloxylation of acetals with cyclic diacyl peroxides

An acetal fragment is a well-known protective group which does not activate the neighboring alpha-position. Selective functionalization of the non-activated acetal alpha-position with formal retaining of the acetal fragment was realized using cyclic diacyl peroxides. The discovered oxidative C-O coupling of cyclic diacyl peroxides with acetals leads to alpha-acyloxy acetals with a free carboxylic acid group in 42-85% yields. The reaction probably proceeds via in situ enol ether formation, oxidative [5 + 2] cycloaddition, and the recovery of the acetal fragment.

Automated summary

The oxidative C-O coupling of cyclic diacyl peroxides with acetals enables the selective functionalization of the non-activated acetal alpha-position. The reaction produces alpha-acyloxy acetals with a free carboxylic acid group in yields ranging from 42-85%.