Synthesis of α-Alkoxycarbonyl-α-siloxyamides by the Reaction of a Carbamoylsilane with α-Ketoesters

Abstract

N,N-Dimethylcarbamoyl(trimethyl)silane reacted with a series of α-ketoesters in anhydrous toluene at 60 ℃ to afford α-alkoxycarbonyl-α-siloxy amide derivatives in good yields (70%～99%). When the alkyl of α-ketoesters was L-2-isopropyl-5-methylcyclohexyl, the reactions possess stereo selectivity. The experimental results showed that the electronic property of the substituted group on the aryl ring affected both the reaction ratio and the yields of products. The structures of the products were characterized by element analysis, 1 H NMR, 13 C NMR and IR spectra. A reaction mechanism is proposed. The mild and no catalyst conditions, simple procedure, less byproducts and good yields provide an effective method for the preparation of α-alkoxycarbonyl-α-hydroxy amides.

Synthesis of 3-Hydroxy-3-heterocyclebutylamide Derivatives Using Carbamoylsilanes as an Amide Source

“…那么是否能通过羰 基所连基团的电子效应对羰基进行影响, 加快反应速 率, 降低 α-活泼氢水解副反应, 实现脂肪酮的加成反应. 沿着这一思路进行了氨甲酰基硅烷与 α-羰基酰胺或酯 的反应, 得到了预期结果 [22,23] . 在 3b、3c'和 3d 的分子中, 氨基的保护基甲氧甲基很容 易在稀盐酸溶液中被水解脱去保护基, 得到 α-羟基仲酰 胺衍生物 [24,34] , 仲酰胺基是连接药物分子、合成肽或合 成杂环化合物中的重要的官能团 [9,35～37] .…”