Dioxygen Activation under Ambient Conditions: Cu-Catalyzed Oxidative Amidation−Diketonization of Terminal Alkynes Leading to α-Ketoamides

Abstract

A novel Cu-catalyzed oxidative amidation-diketonization reaction of terminal alkynes leading to alpha-ketoamides has been developed. This chemistry offers a valuable mechanistic insight into this novel Cu catalysis via a radical process. O(2) not only participates as the ideal oxidant but also undergoes dioxygen activation under ambient conditions in this transformation.

A simple, efficient, regioselective and one-pot preparation of N-hydroxy- and N–O-protected hydroxyindoles via cycloaddition of nitrosoarenes with alkynes. Synthetic scope, applications and novel by-products

“…Compounds 12b and 12c were characterized and spectra and analyses are in agreement with data previously reported in literature. 40 Compound 16a and compound 16b show the same spectroscopic data reported in literature. 43 …”

“…In a previous report by Jiao the same -ketoamide compounds and analogues were prepared by copper-catalyzed oxidative amidation-diketonization of terminal alkynes. 40 Conversely, no traces of 12a were detected in the reaction between 4-nitronitrosbenzene and 1-bromo-2-phenylacetylene.…”

Iodine-Catalyzed One-Pot Synthesis ofα-Ketoamides from Unsaturated Hydrocarbons

“…关于 α-酮酰胺的合成已有很多报道 [2] , 其合 成方法主要包括以下几种: (1)铜催化的苯乙炔或苯乙醛 的氧化酰胺化反应 [3] ; (2)铜或银催化的 α-酮酸与甲酰胺 或叔胺的氧化缩合反应 [4] ; (3)钯或铜催化的芳基卤化物 的插羰酰胺化反应 [5] ; 以及 (4) 7] , TBHP [8] , I 2 /NBS [9] 表 1 合成 α-酮酰胺反应条件的优化 [11] ; 二是苯乙烯与碘反应生成碘鎓离子, 然后再 [13] (Scheme 1). …”

Oxidative cross-dehydrogenative coupling of amines and α-carbonyl aldehydes over heterogeneous Cu-MOF-74 catalyst: A ligand- and base-free approach

“…Recently, aerobic oxidative cross-dehydrogenative coupling transformations have exhibited several advantages in the construction of -ketoamides. Jiao and Zhang previously reported an approach to -ketoamides by the CuBr 2 -catalyzed oxidative amidationdiketonization reaction of terminal alkynes using oxygen as the oxidant and as a reactant via dioxygen activation [11]. Jiao and co-workers subsequently changed the synthetic strategy to the CuBr-catalyzed aerobic oxidative coupling of aryl acetaldehydes with anilines [1].…”