催化合成γ-酮酯的新反应研究

Study on Catalytic Synthesis of γ-Ketoesters

研究了在铜盐催化剂的作用下,芳基重氮乙酸甲酯与烯胺能够发生一种新型加成反应。该反应并不产生预期的环丙烷化合物,而是以较高的收率产生γ-酮酯化合物。我们详细考察了芳基重氮化合物的结构、反应溶剂以及催化剂对这一反应的影响。结果表明,在反应中所实验的芳基和杂环芳基重氮乙酸酯都能以较高的收率得到γ-酮酯,反应溶剂对反应结果影响不大,在所测试的催化剂中,Cu(hfacac)2由于相对廉价并且能以较好的收率得到γ-酮酯,是最好的催化剂。所得化合物经1H NMR1、3C NMR、HRMS(EI+)测试技术进行表征。

The reaction of aryldiazoacetates with enamine catalyzed by copper complexes provided γ-keto esters in good yields.None of the expected aminocyclopropane product was found after careful examination of the reaction mixture.A detailed investigation of the effects of,aryldiazoacetates,solvents and catalyst on the reaction was carried out.The results indicated that all aryl-and heteroaryl-diazoacetates examined in the reaction gave good yields of γ-keto esters,and all tested solvents provided good yields.Cu（hfacac）_2 was preferred due to its excellent yield and relative low price in most tested catalysts.The products obtained were characterized by（）^（1）H NMR、（）^（13）C NMR、HRMS（EI~＋）.