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基于氯过氧化物酶(CPO)对有机底物的手性识别,以CPO催化、叔丁基过氧化氢(TBHP)氧化3-氯丙烯合成手性(R)-环氧氯丙烷,并引入多羟基化合物为添加剂提高了目标产物的产率及对映选择性.反应主要受体系的pH值以及CPO用量等因素控制.UV-vis及CD光谱分析表明,反应体系中引入多羟基化合物(甘油、PEG400、PEG600)时,CPO的血红素辅基暴露程度增加,底物容易接近活性中心,同时CPO的α-螺旋结构得以加强,从而有效提高了产物收率.CPO对底物的手性识别主要基于底物与酶催化中间体([Fe(IV)=O·]+)形成的复合物对酶的稳定性的影响.通过反应条件优化,(R)-环氧氯丙烷产率可达67.3%,对映选择性(ee)97.5%.
Based on chiral recognition of chloroperoxidase (CPO) for organic substrates, chiral (R) -epichlorohydrin was synthesized by oxidation of 3-chloropropene with CPO catalysis and t-butyl hydroperoxide (TBHP) The polyhydroxyl compounds as additives increased the yield and enantioselectivity of the target product.The reaction was mainly controlled by the pH of the system and the amount of CPO.The UV-vis and CD spectra showed that the introduction of polyhydroxy compounds (glycerin , PEG400, PEG600), CPO heme cofactor exposure increased, the substrate easily accessible to the active center, while CPO α-helical structure was strengthened, thus effectively increasing the yield of products .CPO chiral recognition of the substrate Based on the effect of the complex formed between the substrate and the enzyme-catalyzed intermediate ([Fe (IV) = O ·] +) on the stability of the enzyme, the yield of (R) -epichlorohydrin was 67.3%, enantioselectivity (ee) 97.5%.