(S)-2-吡咯烷基甲醇衍生物催化α,β-不饱和酮的不对称环氧化反应  

Asymmetric Epoxidation of α,β-Enones Catalyzed by Chiral Pyrrolidinylmethanol Derivatives

作　　者：柳文敏[1] 王巧峰[2] 刘雪英[2] 张生勇[2] 

机构地区：[1]南阳师范学院化学与制药工程学院,南阳473061 [2]第四军医大学药学系化学教研室

出　　处：《应用化学》2007年第8期925-928,共4页Chinese Journal of Applied Chemistry

基　　金：国家自然科学基金(20572131)资助项目

摘　　要：采用以L-脯氨酸为原料合成的5种手性β-氨基醇作为有机小分子催化剂,用于催化α,β-不饱和酮的不对称环氧化反应。考察了影响对映选择性的催化剂结构、氧化剂种类、溶剂、反应温度等因素。结果表明,催化剂的结构、氧化剂的种类、反应的溶剂对对映选择性和化学产率影响较大,而反应温度在室温至-20℃范围内,对反应的对映选择性和化学产率影响不明显。当以叔丁基过氧化氢(TBHP)为氧化剂、正己烷为溶剂、在室温下、以(S)-2-吡咯烷-α,α-二(α-萘基)甲醇(2b)作催化剂时,所得环氧化物的对映体过量最高为84.6%e.e.,产率最高为89.7%。通过1H NMR对所得环氧化物4的结构进行了表征,并利用手性色谱柱通过高效液相色谱法(HPLC)对产物4的对映体过量进行了测定。Five chiralβ-amino alcohols were prepared from （S） -proline in an efficient manner and applied in the organocatalytic asymmetric epoxidation of α,β-enones. The effect of the catalyst structure, oxidant, solvent and reaction temperature on enantioselectivity was also studied. The results show that the catalyst structure, oxidant and solvent were important for the stereoselectivity and the conversion. However, the change in the enantioselectivity was not obvious when the reaction temperature was decreased from room temperature to -20 ℃. When tea-butyl hydroperoxide（TBHP） was used as the oxidant, and hexane as the solvent, at room temperature, （S）-2-（di-ot-naphthylhydroxymethyl） pyrrolidine 2b was successfully applied in the organocatalytic asymmetric epoxidation of α,β-enones with good yield and up to 84. 6% enantiomeric excess. The structure of compound 4 was confirmed by ^1 H NMR, and the e. e. values were determined by HPLC analysis on chiral columns.

关 键 词：环氧化反应 手性Β-氨基醇 不对称催化 Α Β-不饱和酮 L-脯氨酸衍生物 

分 类 号：O643.3[理学—物理化学]