Part I: Novel Reactions of Oxoammonium Salts in the Presence of Base Part II: Behavior of Ketones and Thioketones with Organometallic Compounds
Date of Completion
In the presence of pyridine, β-alkoxy alcohols are oxidized with oxoammonium salts to give dimeric esters; however, in the presence of 2,6-disubstituted pyridines, β-alkoxy alcohols are oxidized to aldehydes in good yields. ^ Aldehydes are normally not oxidized by oxoammonium salts. However, in the presence of pyridine, aldehydes form a betaine complex, which is oxidized by the oxoammonium cation to an acylpyridinium salt. This acylpyridinium intermediate may react with another equivalent of the aldehyde to form stable salts or may be trapped by addition of an alcohol to give a moderate yield of ester. The competing reaction with the starting aldehyde prevents a full conversion to the ester.^ Main-group organometallic compounds react differently with ketones and thioketones. Whereas organolithiums and alkylmagnesium halides add to the carbonyl carbon of ketones to give tertiary alcohols, the main reaction with thioketones is reduction to afford a thiol. The reactions of organometallic compounds with adamantanethione were investigated.^
Bartelson, Ashley Lynn, "Part I: Novel Reactions of Oxoammonium Salts in the Presence of Base Part II: Behavior of Ketones and Thioketones with Organometallic Compounds" (2011). Doctoral Dissertations. AAI3485252.