Autoxidation of ketones and esters in basic solution

Abstract

The first contribution t o the alkaline autoxidation of ketones was by Doering and Haines who, using t-butyl alcohol and potassium tbutoxide as solvent and base, respectively, obtained acids and aldehydes as the products. Scheme 1 was postulated t o account for the results:

Synthetic studies toward (+)-cortistatin A

“…xlvi Enolate peroxidation by O 2 has also been suggested to proceed through a chain-reaction-based radical pathway. xlvii …”

Synthesis of 10β,17α-Dimethyl-17β-(1,2-dioxopropyl)estra-5,9-diene-3-ketal

“…The formation of the ketone at the C 21 position probably results from the addition of O 2 to the anion R -. [16] The new steroid A-Me, isolated in 70% yield as a yellow powder (m.p. 140-141°C) was fully characterised.…”

Selective Chemical Oxidation of Risperidone: A Straightforward and Cost‐Effective Synthesis of Paliperidone

“…This reaction is probably slow, as demonstrated in the literature that dioxygen oxidation of enolates may be stopped, under appropriate circumstances, at the hydroperoxide level. [23][24][25][26] The low reduction rate of 19 allows, through an intramolecular process, the conversion to ketone 12. As already stated, 12 is not a useful intermediate.…”