α-羰基酰氯与氨甲酰基硅烷反应合成连三羰基化合物的新方法

Novel Method for Synthesis of Vicinal Tricarbonyl Compounds from α-Ketoacid Chlorides and Carbamoylsilanes

连三羰基化合物在生物学、药物化学和化学合成中是一类重要的化合物,他们的合成方法被广泛的研究.本文报道了一种新的合成方法,即用氨甲酰基硅烷与一系列α-羰基酰氯或草酸二酰氯在无水无氧、0℃和甲苯作溶剂的条件下反应,合成连三羰基化合物的方法.反应生成的连三羰基化合物的结构用元素分析、1H NMR和13C NMR等方法进行了表征.通过研究发现,在氨甲酰基硅烷与草酰氯的反应中,发生了脱羰基放出了CO,不生成连四羰基化合物.该方法反应温和,操作简单,不使用氧化剂,可操作性较强,具有重要的合成应用价值.

Vicinal tricarbonyl compounds are a very important class of organic compounds in biology, phar- maceutical chemistry and chemical synthesis, whose synthesis methods have been investigated extensively. Here, we report a novel synthetic method by carhamoylsilanes reacted with a series of α-keto acid chlorides or oxalyl chloride in toluene under anhydrous condition at 0℃ leading to formation of vicinal tricarbonyl compounds. The structures of vicinal tricarbonyl compounds were characterized by element analysis, ^1H NMR and ^13C NMR spectra. The experimental results showed that the reaction of carbamoylsilanes and oxalyl chloride did not give vieinal tetracarbonyl compounds, which accompanied by decarbonylation and gave out CO. The mild and simple procedure, free oxidants and simple operation provides a valuable method for the preparation of various vicinal tricarbonyl compounds.