Oxidation of β-Ketoamides: The Synthesis of Vicinal Tricarbonyl Amides

Abstract

A facile and direct oxidative reaction for the synthesis of vicinal tricarbonyl amides in moderate to excellent yields (53-88%) was developed starting from readily available β-ketoamides in the presence of phenyliodine(III) bis(trifluoroacetate). The resulting products possess significant synthetic potential, making this approach a valuable addition to the group of traditional methods already available for the preparation of these molecules.

β‐Keto Amides: A Jack‐of‐All‐Trades Building Block in Organic Chemistry

“…The direct oxidation of β ‐keto amides 356 to 357 have also been achieved by DDQ/TEMPO, [160] Dess ‐ Martin periodinane (DMP), [161] Fe(NO 3 ) 3 /PhI=O [162] or PhI(COOCF 3 ) 2 (PIFA) [163] . Trivalent iodine compounds are versatile oxidants for the α ‐acyloxylation of β ‐keto amides to give 358 and 359 (Scheme 71).…”

Gold(I)-Catalyzed Oxidation of Acyl Acetylenes to Vicinal Tricarbonyls

“…Conventional routes to VTCs include oxidation of β-dicarbonyl compounds − or their α-mono­(di)­substituted derivatives , (Scheme a) and oxidative cleavage of the C=C, C=N, C=S, C=P, and C=I double bonds of α-functionalized β-dicarbonyls , (Scheme b). One of the most convenient and frequently used methods leading to VTCs is the oxidation of diazo derivatives of β-dicarbonyls (X = N 2 ) by t -BuOCl, , DMDO, epoxides, or pyridine N -oxides .…”

“…To the best of our knowledge, isolation of aliphatic VTCs is often complicated probably because of easy side aldol condensations. , Our attempts to obtain alkyl-substituted products of satisfactory purity failed. Hence, more stable heterocyclic derivatives of aliphatic VTCs were chosen for characterization.…”

Aza-Riley Oxidation of Ugi-Azide and Ugi-3CR Products toward Vicinal Tricarbonyl Amides: Two-Step MCR-Oxidation Methodology Accessing Functionalized α,β-Diketoamides and α,β-Diketotetrazoles

“…19 One step direct oxidation is more attractive, of which previous methods involving organoiodine-chemistry have recently been improved upon. 20,21…”

“…The most common is indirect oxidation of β-diketones by Regitz diazo transfer/oxidation with t -BuOCl or DMDO . One step direct oxidation is more attractive, of which previous methods involving organoiodine-chemistry have recently been improved upon. , …”