基于拟肽仿生催化作用的α,β-不饱和环酮合成及机理研究  

Study on the synthesis and reaction mechanism ofα,β-unsaturated cyclic ketones based on biomimetic catalysis with enzyme-like tetrapeptides

作　　者：李卫平 白婷 LI Wei-ping;BAI Ting(Gansu Key Laboratory of Fine Chemicals,Lanzhou 730000,China;Gansu Insititute of Chemical Industry,Lanzhou 730000,China)

机构地区：[1]甘肃省精细化工重点实验室,甘肃兰州730000 [2]甘肃省化工研究院有限责任公司,甘肃兰州730000

出　　处：《化学研究与应用》2022年第6期1349-1356,共8页Chemical Research and Application

基　　金：甘肃省创新基地和人才计划-青年科技基金计划项目(1506RJYA136)资助;甘肃省精细化工重点实验室项目(18JR2RA021)资助。

摘　　要：首次通过人工合成的具有β-转角结构的拟肽,模仿脱水酶催化β-羟基环酮化合物的分子内脱水,制备α,β-不饱和环酮,实验结果表明:在生理温度(37℃)条件下,拟肽催化剂对于β-羟基环酮衍生物具有优异的催化性能和反应收率。其中,β-羟基环戊酮类化合物的催化脱水产率最高可达96%,β-羟基环己酮类化合物的催化脱水产率最高可达97%。同时,对β-羟基酮仿生催化脱水形成α,β-不饱和酮的反应机理进行了研究。For the first time,the tetrapeptides were used to imitate the dehydratases to catalyze the intramolecular dehydration ofβ-hydroxy cyclic ketones to furnish theα,β-unsaturated cyclic ketones.At physiological temperature(37℃),the tetrapeptides displayed excellent catalytic activities and achieved high yields.The dehydration reaction ofβ-hydroxy cyclopentanone derivatives,β-hydroxy cyclohexanone derivatives afforded up to 96%,97%yield,respectively.Meanwhile,the biomimetic intramolecular dehydration reaction mechanism ofβ-hydroxy cyclic ketones catalyzed by enzyme-like tetrapeptides was studied.

关 键 词：β-转角 拟肽 β-羟基环酮衍生物 α β-不饱和环酮 

分 类 号：O629.72[理学—有机化学]