反式2,3-二芳基取代-1-氨基环丙烷羧酸的合成及其结构研究

Study on the Highly Diastereoselective Synthesis and Structure of trans-2,3-Diaryl Substituted 1-Aminocyclopropanecarboxylic Acid Derivatives

芳香醛与马尿酸在Erlenmeyer反应条件下缩合得到 (Z) 2 苯基 4 芳亚甲基 5 ( 4H) 唑酮 ,然后在室温下与芳基重氮甲烷通过非对映高立体选择性 1,3 偶极环加成反应得到螺环化合物 ,再经醇解开环、水解去保护合成出反式 2 ,3 二芳基 1 氨基取代环丙烷羧酸 .通过元素分析 ,IR ,1HNMR ,13 CNMR ,MS和X射线晶体测定 ,确认了它们的化学结构和立体构型 .实验结果表明 ,通过选择适当的芳香醛和芳基重氮甲烷 ,可以得到不同立体构型的反式 2 ,3 二芳基取代 1 氨基环丙烷羧酸 .

(Z)-2-Phenyl-4-arylidene-4, 5-dihydro-oxazol-5-ones were synthesized by condensation of hippuric acid and aromatic aldehyde following the Erlemneyer procedure, then reacted with aryldiazomethane in a highly diastereoselective 1,3-dipolar cycloaddition at room temperature to give spirocyclopropane derivatives in 86% similar to 90% yields. The spirocyclopropane derivatives were readily converted into the corresponding trans-2,3-diaryl-1-aminocyclopropanecarboxylic acid by treatment with absolute methanol containing catalytic amounts of sodium methoxide, then hydrolysis in 4 mol/L of HCl/HOAc. The structures and configurations were established on the basis of their elemental analyses and spectroscopic data, such as IR, H-1 NMR, C-13 NMR, MS and X-ray crystallography. The results indicated that 2, 3-diaryl-1-aminocyclopropanecarboxylic acids' with desired configurations could be synthesized with certain aromatic aldehyde and appropriate aryldiazomethane.