(S)-(+)-2,2-二甲基环丙烷甲酰胺的不对称合成  

Asymmetric Synthesis of( S)-( + )-2,2-dimethylcyclopropane Carboxamide

作　　者：张华林[1] 姚建华[1] 任春梅[2] 雷武[1] 夏明珠[1] 王风云[1] 

机构地区：[1]南京理工大学工业化学研究所,江苏南京210094 [2]南京化工职业技术学院,江苏南京210048

出　　处：《合成化学》2015年第5期423-427,共5页Chinese Journal of Synthetic Chemistry

摘　　要：以环己二胺作为手性源,与3,5-二叔丁基水杨醛经缩合反应制得Salen配体(R,R)-N,N'-二(3,5-二叔丁基水杨醛)-1,2-环己二胺(6);甘氨酸乙酯盐酸盐经重氮化和6与三氟甲烷磺酸亚铜催化的不对称环丙烷化反应制得(S)-(+)-2,2-二甲基环丙烷甲酸乙酯(9);9经水解、酰氯化和氨解反应合成了(S)-(+)-2,2-二甲基环丙烷甲酰胺,ee值82%,总收率55.4%,其结构经1H NMR和IR确证。A Salen ligand（ 6） was prepared by condensation reaction of chiral diaminocyclohexane with 3,5-ditertbutyl-salicylaldehyde.（ S）-（ ＋）-2,2-dimethylcyclopropane carboxylic acid ethyl ester（ 9） was obtained by diazotization and asymmetric cyclopropanation catalyzed by 6 and copper（ Ⅰ）triflate from glycine ethyl ester hydrochloride.（ S）-（ ＋）-2,2-dimethylcyclopropane carboxamide with an overall yield of 55. 4% and 82% ee was synthesized eventually by hydrolysis,chlorization and ammonolysis from 9. The structure was confirmed by1 H NMR and IR.

关 键 词：SALEN配体 重氮乙酸乙酯 环丙烷化 (S)-(+)-2 2-二甲基环丙烷甲酸乙酯 (S)-(+)-2 2-二甲基环丙烷甲酰胺 不对称合成 

分 类 号：O621.3[理学—有机化学] O624.5[理学—化学]