光/氧化还原酶协同催化的不对称合成研究进展  

Research Progress on Asymmetric Synthesis with Photo/Oxidoreductase Synergistic Catalysis

作　　者：卓宇晴 崔宝东 ZHUO Yuqing;CUI Baodong(College of Pharmacy,Zunyi Medical University,Zunyi 563003,China)

机构地区：[1]遵义医科大学药学院,贵州遵义563003

出　　处：《合成化学》2024年第4期369-380,392,共13页Chinese Journal of Synthetic Chemistry

基　　金：国家自然科学基金资助项目(22261056,21907114);贵州省科技厅平台人才项目(黔科合平台人才-GCC[2022]032-1)。

摘　　要：氧化还原酶是一类重要的酶,它可以将氧化还原反应进行转换。含有黄素和烟酰胺的酶如酮还原酶、烯烃还原酶等氧化还原酶可以在光能的激发下产生自由基中间体,从而引发进一步的转化反应,还能引发酶的非天然反应活性,获得新酶催化功能。这种光/氧化还原酶协同催化比单一的光催化和酶催化更能实现具有挑战性的反应。光/酶协同催化研究虽然处于发展的初期,但是在可见光与烯烃还原酶催化解锁酶的非天然反应研究领域展现出了广阔的应用前景。本文围绕光/氧化还原酶协同催化的不对称合成应用,重点介绍了其在烯烃异构化/不对称还原反应、α-乙酰氧基苯并环己酮的不对称还原反应、烯烃/酮/烯酰胺的不对称还原反应、β-烷基取代的环己酮原位消旋化/不对称还原反应和分子内/分子间的不对称氧化还原偶联反应方面的相关研究进展。Oxidoreductases are an important class of enzymes that can catalyze various redox reactions.Flavins or niacinamide containing enzymes including the keto-reductases and olefin reductases can catalyze to generate the free radical intermediates under the excitation of light energy,thus inducing the further conversions.They can also trigger the unnatural reaction activity of enzymes and acquire new catalytic functions.The photo/oxidoreductase co-catalysis can be able to promote the traditional challenging reactions comparing with the single photocatalysis or enzyme catalysis.Although photo/enzyme synergetic catalysis is still in its early stages of development,it has already shown broad application prospects.This review is based on the application of photo/oxidoreductase co-catalysis in asymmetric synthesis,which mainly focus on the research progress in olefin isomerization/asymmetric reduction reactions,asymmetric reduction reactions ofα-acetoxybenzocyclohexanones,asymmetric reduction reactions of olefins/ketones/enamides,asymmetric in-situ racemization/reduction reactions ofβ-alkyl substituted cyclohexanones,asymmetric intramolecular/intermolecular redox coupling reactions.

关 键 词：氧化还原酶 光催化 酶催化 协同催化 烯烃还原酶 不对称还原反应 

分 类 号：O626[理学—有机化学]