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

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.