An acyloin-type rearrangement is an acid-catalyzed reorganization of α-hydroxy ketones (13.31), also known as acyloins (Scheme 13.14). These acid-catalyzed [1,2]-alkyl migration reactions also can involve other types of molecules, such as glycols (pinacol rearrangement), α-diketones (benzil–...
Treatment of acetophenones with thallium(III) nitrate in acidic methanol is shown to result in smooth oxidative rearrangement to give methyl arylacetates in moderate to excellent yields. The scope and limitations of the synthesis have been defined and the mechanism of the transformation studied by...