Synthesis of α-Keto-Imides via Oxidation of Ynamides

Abstract

A de novo preparation of α-keto-imides via ynamide oxidation is described. With a number of alkyne oxidation conditions screened, a highly efficient RuO2-NaIO4 mediated oxidation and a DMDO oxidation have been identified to tolerate a wide range of ynamide types. In addition to accessing a wide variety of α-keto-imides, the RuO2-NaIO4 protocol provides a novel entry to the vicinal tricarbonyl motif via oxidation of push-pull ynamides, and imido acylsilanes from silyl-substituted ynamides. Chemoselective oxidation of ynamides containing olefins can be achieved using DMDO, while the RuO2-NaIO4 protocol is not effective. These studies provide further support for the synthetic utility of ynamides.

Visible light-induced transition metal-catalyzed transformations: beyond conventional photosensitizers

“…25 Although vast literature precedents exist for this exact synthetic approach, they typically employ: 1) expensive metal catalyst (Ru, Au); 2) stoichiometric oxidants; and are 3) conducted at high temperatures. 26 Hwang’s method precludes the needs of the above requirements by utilizing cheap Cu-catalyst, abundant O 2 as oxidant, and sustainable light sources. The scope of the reaction is quite general, as α -ketoimides and α -ketoamides possessing sensitive functionalities, such as halogens, cyano, ester groups, were well tolerated ( 58a – i , 59a – d ).…”

SeO2 mediated efficient synthesis of amides and α-ketoamides of secondary amines with wide substrate scope

“…1 pharmaceuticals (rapamycin, enzyme inhibitors) and agrochemicals (FK506). 2-4 α-Ketoamides are synthesized from diverse substrates such as methyl-ketones, 5-10 aldehydes/arylglyox-als, [11][12][13][14][15][16] -ketoacids, [17][18][19][20] terminal alkynes, [21][22][23][24] cyanamides, 25 carbamoyl stannane/ silane with acid chlorides, [26][27][28] addition of aroyl to aryl-acetamides, 29 2,2-dibromo-1-aryl ethanones 30 and double carbonylation of aryl iodides. [31][32][33] Usually in these oxidative amidation, a co-oxidant is required.…”

Palladium Catalyzed Oxidation of Ynamides Using Dimethyl Sulfoxide as Oxidant: A Facile Way to Synthesizeα-Ketoamide Derivatives

“…88～90 ℃(文献值 [19] : 89～91 8, 146.9, 135.9, 135.8, 135.7, 134.2, 131.1, 130.9, 130.1, 129.8, 129.3, 129.1, 49.6, 22.9. 9, 160.6, 146.8, 136.0, 135.6, 134.2, 131.1, 131.1, 130.9, 130.1, 129.7, 128.0, 115.1, 56.5, 49.2, 22.9;IR (KBr) ν: 3062, 3003, 2969, 1677, 1610, 1597, 1363, 1214, 1165, 1091 1, 135.7, 134.1, 132.0, 131.3, 131.0, 130.1, 129.8, 120.7, 48.5, 23.0.…”

“…近年来, 炔酰胺的氧化已经成为构建 α-酮酰胺的重 要方法. 2008 年 Al-Rashid 等 [19] 报道了炔酰胺可被 RuO 4 或过氧丙酮(DMDO)氧化体系氧化高产率地得到 α-酮酰 胺, 但这两种氧化剂都需要大大过量, 且不易保存. 2014 年朱红军 [20] 和 Iwasawa [21] 研究小组分别报道了过 化下以二甲亚砜为氧化剂通过炔酰胺的氧化反应高产 率地合成 α-酮酰胺的新方法.…”