发布时间：2024-03-11

文章标题：祝贺本课题组博士生申倩倩与张武元教授课题组合作的最新论文被Angewandte Chemie录用 2024-03-12

内容：

Peroxygenase Enabled Reductive Kinetic Resolution for the Enantioenrichment of Organoperoxides

Qianqian Shen [a],[b] , Juzhang Yan [a] , Yuchen Han [a] , Zaoxiao Zhang [b]* , Huanhuan Li [a] , Dulin Kong [c] , Jianjun Shi [d] , Chengsen Cui [a]* , Wuyuan Zhang [a]*

 

Abstract:

Enantiomerically pure organoperoxides serve as valuable precursors in organic transformations. In this study, we present the first examples of unspecific peroxygenase-catalyzed kinetic resolution of racemic organoperoxides through asymmetric reduction. Through meticulous investigation of the reaction conditions, it is shown that the unspecific peroxygenase from Agrocybe aegerita (AaeUPO) exhibits robust catalytic activity in the kinetic resolution reactions of the model substrate with turnover numbers up to 60000 and turnover frequency of 5.6 s -1 . Various aralkyl organoperoxides were successfully resolved by AaeUPO, achieving excellent enantioselectivities (e.g., up to 99% ee for the (S)-organoperoxide products). Additionally, we screened commercial peroxygenase variants to obtain the organoperoxides with complementary chirality, with one mutant yielding the (R)- products. While unspecific peroxygenases have been extensively demonstrated as a powerful oxidative catalyst, this work highlights its usefulness in catalyzing the reduction of organoperoxides and providing versatile chiral synthons.

 

https://onlinelibrary.wiley.com/doi/10.1002/anie.202401590

 

过氧合酶催化还原动力学拆分合成对映体富集的有机过氧化物

 

摘要：

对映体纯的有机过氧化物作为有机转化中有价值的前体。在此，我们介绍了非特异性过氧合酶通过不对称还原催化动力学拆分外消旋有机过氧化物的第一个实例。通过对反应条件的细致研究，表明AaeUPO的非特异性过氧合酶在模型底物的动力学拆分反应中表现出优异的催化活性，周转次数达60000，周转频率为5.6s-'。AaeUPO成功地实现了各种芳烷基有机过氧化物动力学拆分，获得了优异的对映选择性(例如：（S）-有机过氧化物产物的ee高达99%。此外。我们筛选了商业过氧合酶变体以获得具有互补手性的有机过氧化物，其中一个突变体产生（R）-产物。虽然非特异性过氧合酶已被广泛证明是一种强大的氧化催化剂，但本研究强调了它们在催化有机过氧化物还原和提供多功能手性合成子方面的实用性。