Copper‐Catalysed (Diacetoxyiodo)benzene‐Promoted Aerobic Esterification Reaction: Synthesis of Oxamates from Acetoacetamides

Abstract

A copper-catalysed (diacetoxyiodo)benzene-promoted aerobic esterification reaction of acetoacetamides was developed for the synthesis of oxamates, which are useful precursors in synthetic organic chemistry. This practical and mild synthetic approach proceeded at 25 8C under open-air conditions and afforded methyl 2-oxo-2-(phenylamino)acetates in good to excellent yields combined with CÀC s-bond cleavage and formal oxidative CÀH bond functionalization. A mechanism is proposed.

Applications of Phenyliodine(III)diacetate in C−H Functionalization and Hetero‐Hetero Bond Formations: A Septennial Update

“…A method for converting cinnamic acids into α-keto diacetates (136) through decarboxylative functionalization was revealed in this work by Du and Zhao et al [127] A facile and straightforward route to the α-keto diacetate framework was made possible by the reaction of cinnamic acids (135) with PIDA in 1,2-dichloroethane in the presence of sulfuric acid (Scheme 47). This included aryl migration, oxygen atom insertion, decarboxylation, and diacetoxylation tandem sequence hypervalent iodine-mediated oxidative process.…”

“…Alcohols (127) worked as the alkoxylating agents, PhI(OAc) 2 as the oxidant, and benzoquinone (BQ) as the co-oxidant to effectively achieve copper-promoted direct CÀ H alkoxylation of S,S-functionalized internal olefins, i. e., α-oxo ketene dithioacetals (126). In this way, the alkoxylated olefins (128) were created by Yu and co-workers and used to synthesize alkoxylated N-heterocycles.…”

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

“…OEt 2 (Scheme 103). Later, they modified the reaction conditions to be milder by using iodobenzene diacetate (PIDA) as the oxidant [229] . In the presence of copper or silver catalysts, β ‐keto amide 507 could be oxidatively cleaved to the corresponding α ‐keto amides 510 by oxygen.…”

Oxamates as 1,2‐Diketone Equivalents: The Effect of Fluorine

“…Oxamates can act as useful precursors in synthetic organic chemistry [13] and material science. Copper‐catalysed (diacetoxyiodo)benzene(PIDA)‐promoted aerobic esterification reactions give straightforward access to oxamates from acetoacetamides (R 1 =H, Me, PhCH 2 , see Figure 3).…”