L-抗坏血酸作为手性元用于手性稠环类化合物合成的研究  

Studies on the Synthesis of Chiral Fused Cyclic Compounds Using L-Ascorbic Acid as a Chiron

作　　者：常新红[1] 王建革[1] 田欣哲[1] 陈庆华[1] 

机构地区：[1]洛阳师范学院化学系,洛阳471022

出　　处：《化学学报》2003年第7期1083-1089,共7页Acta Chimica Sinica

基　　金：国家自然科学基金(No.29672004)

摘　　要：研究了L-抗坏血酸和甲基乙烯酮不对称反应的控制条件以及后处理方法,经重结晶后得到了产率高(71％)、光学纯度高(≥98％ee)的二环内酯类衍生物3.通过化学/物理方法、X射线晶体测定了化合物3的物理常数、化学结构、立体化学以及晶体结构.在此基础上,化合物3分别在氯化氢/无水醇介质中(CH_3OH,C_2H_5OH)进一步反应,通过分子内差向异构化/羟醛缩合/亲核脱水反应分别得到了新的含有多个官能团和多个手性中心的稠环类化合物4a和4b.此研究结果可以为L-抗坏血酸手性元在不对称合成中应用,为具有生物活性的复杂化合物的合成提供新的途径.The reaction conditions and work-up method of the asymmetric reaction of L-ascorbic acid with methyl vinyl ketone have been investigated. After recrystallization of the crude product, the fused cyclic lactone derivative 3 was obtained in 71% yield and greater than or equal to98% ee. The physical constants, chemical structure, stereochemistry and crystal structure of compound 3 were determined and characterized by chemical and physical methods and X-ray crystallography. Based on these results, compound 3 was further treated with the 2% methanolic or ethanolic HCl solution as a reaction medium to afford the novel functionalized cyclic compounds 4a and 4b, respectively. The results provide a valuable synthetic route to the application of L-ascorbic acid in its asymmetric synthesis and an important synthetic strategy for some chiral compounds of, biological interests.

关 键 词：L-抗坏血酸 手性元 手性稠环类化合物 合成 研究 化学结构 晶体结构 

分 类 号：O629[理学—有机化学]