Photochemistry of Substituted Benzoylformate Esters. A Convenient Method for the Photochemical Oxidation of Alcohols

Article abstract of DOI:10.1021/jo00113a029

The production of aldehydes and ketones via photochemical hydrogen atom transfer in substituted benzoylformate esters of primary and secondary alcohols has been investigated.Substituent effect studies have shown that (2,4-dimethoxybenzoyl)formate (DMBF) esters give superior performance.A divergence in the byproducts derived from the ester group (the benzaldehyde (and presumably CO) or the benzoic acid (and presumably CO2)) is observed depending on the presence of oxygen.A mechanistic rationale for the benzoic acid has been advanced based on the known trapping of intermediate 1,4-biradicals by oxygen followed by fragmentation.