Oxone-Mediated Oxidative Cleavage of β-Keto Esters and 1,3-Diketones to α-Keto Esters and 1,2-Diketones in Aqueous Medium

Abstract

A versatile and highly efficient method for the direct synthesis of α-keto esters and 1,2-diketones has been developed. This approach utilizes the oxidative cleavage of a variety of β-keto esters and 1,3-diketones mediated by an Oxone/aluminum trichloride system. The simple one-step oxidation reaction proceeded selectively in aqueous media to afford products in high yields, short reaction times, and environmentally benign conditions.

Diverse synthesis of pyrano[2,3-b]indol and dihydropyrano[2,3-b]indol via tunable Lewis bases catalyzed domino reactions

“…Isatin, 5-methylindoline-2,3-dione, 5-methoxyindoline-2,3-dione, 5-nitroindoline-2,3-dione, 6-(trifluoromethyl)indoline-2,3-dione and 5-chloroindoline-2,3-dione were purchased from commercial sources and were used without further purification. 5-fluoroindoline-2,3-dione, 10 6-methoxyindoline-2,3-dione, 11 6-bromoindoline-2,3-dione, 12 5-bromoindoline-2,3-dione, 10 allenoates 13 and ylide 14 were prepared according to the literature. Nacetyl isatin and substituted N-acetyl isatins were synthesized according to literature procedures.…”

Iodine-Mediated Oxidative Rearrangement of α,β-Unsaturated Diaryl Ketones: A Facile Access to 1,2-Diaryl Diketones

“…2f 1,2-Diketones are widely used in organic chemistry as precursors for the synthesis of chiral alcohols, 3 diols, 4 carboxylic acids, 5 heterocyclic compounds, 6a,2d as well as for the construction of compounds having electronic and photochemical properties in material chemistry. 6b,6c The importance of 1,2-diketones has gained attention in the last few decades; some metal and metal-free methods have been reported to synthesize them using phenyl ketone, 7 alkene oxidation, 8 alkyne oxidation, 9 oxidative cleavage of 1,3-diketone, 10 and benzyl phenyl ketone oxidation using SeO 2 . 11 Further, Mn(III) or Cu mediated oxidative decarboxylative coupling of aryl boronic acids or aryl iodides with aryl propionic acids.…”

Oxone®-Mediated Direct α-Hydroxylation of β-Dicarbonyl Compounds: Racemic Synthesis of Harzialactone A

“…On the other hand, treating β-dicarbonyl compounds with a combination of Oxone ® and AlCl 3 led to 1,2-diketones through unexpected oxidative cleavage. 17 As far as we are aware, there is no precedent for the preparation of α-hydroxy malonates using Oxone ® as the oxidizing agent.…”