三种手性邻二醇的不对称合成及手性高效液相色谱分析  

Asymmetric synthesis and chiral HPLC analysis of three chiral vicinal diols

作　　者：匡永清[1] 张生勇[1] 孙晓莉[1] 尉琳琳[1] 

机构地区：[1]第四军医大学基础部化学教研室,陕西西安710033

出　　处：《第四军医大学学报》2002年第10期865-867,共3页Journal of the Fourth Military Medical University

基　　金：国家自然科学基金资助课题 (2 0 0 0 2 0 0 8)

摘　　要：目的　立体选择性地合成 (1R,2 R) - (+) - 1,2 -二苯基 - 1,2 -乙二醇 (A ) ,(S) - (+) - 3-萘氧基 - 1,2 -丙二醇 (B)和(R) - (- ) - 1-苯基 - 1,2 -乙二醇 (C) .方法　以 t Bu OH/H2 O(1∶1)为溶剂 ,以 K3Fe(CN ) 6 为共氧化剂 ,用 DHQD- PHAL -OPEG- OMe/Os O4 分别催化反式二苯乙烯、萘基烯丙基醚和苯乙烯的不对称二羟基化反应 .反应结束后 ,通过萃取、沉淀和过滤来回收配体 .滤液减压蒸干得粗产物 ,进一步用柱层析分离得纯品 .产物用比旋光度法和核磁共振光谱法鉴定 ,其光学纯度用手性高效液相色谱法测定 .结果　产物的比旋光度和 1H核磁共振光谱 (1 H NMR)与相应二醇的化学结构相符 . A,B,C的对映体过量值 (enantiomer excess,ee)分别为 99% ,90 %和 82 % .结论　 DHQD- PHAL- OPEG- OMe/Os O4 可有效催化烯烃的不对称二羟基化反应 ,制备手性邻二醇 .对反式 - 1,2 -二取代烯烃的立体选择性优于单取代烯烃 .AIM To stereoselectively synthesize (1R, 2R) (+) 1,2 diphenyl 1,2 ethanediol (A), (S) (+) 3 naphthoxy 1,2 propanediol (B) and (R) ( ) 1 phenyl 1,2 ethanediol (C). METHODS The asymmetric dihydroxylations of trans stilbene, naphthyl allyl ether and styrene were catalyzed by DHQD PHAL OPEG OMe/OsO 4 with tBuOH H 2O (1∶1) as the solvent and K 3Fe(CN) 6 as the cooxidant. When the reaction was finished, the ligand was recovered by extraction, precipitation and filtration. The filtrate was evaporated to dryness under a reduced pressure to give the crude product, which was further purified by chromatography to afford the diol. All the products were characterized by optical rotation and 1H NMR. The enantiomer excess (ee) values of the diols were determined by chiral HPLC analysis. RESULTS The optical rotations and 1H NMR spectrum of the products were in agreement with the chemical structures of the corresponding diols. The ee values of A, B, and C were 99%, 90%, and 82% respectively. CONCLUSION DHQD PHAL OPEG OMe/OsO 4 can effectively catalyze the asymmetric dihydroxylation of olefins to form chiral vicinal diols. The enantioselectivity for trans 1,2 disubstituted olefins is better than that for mono substituted olefins.

关 键 词：反式二苯乙烯 萘基烯丙基醚 苯乙烯 不对称二羟基化 手性邻二醇 高压液相色谱法 

分 类 号：O622.3[理学—有机化学]