Li Jiacheng, Duran Cristina, Pogrányi Balázs, Cornish Katy A S, Cartwright Jared, Osuna Sílvia, Unsworth William P, Grogan Gideon
Department of Chemistry, University of York, Heslington, YO10 5DD, York, U.K.
Institut de Química Computacional i Catàlisi and Departament de Química, c/ Maria Aurèlia, Capmany 69, 17003, Girona, Spain.
Angew Chem Int Ed Engl. 2025 Mar 17;64(12):e202422241. doi: 10.1002/anie.202422241. Epub 2024 Dec 18.
Unspecific peroxygenases (UPOs) catalyze the selective oxygenation of organic substrates using only hydrogen peroxide as the external oxidant. The PaDa-I variant of the UPO from Agrocybe aegerita catalyses the oxidation of Z- and E-allylic alcohols with complementary selectivity, giving epoxide and carboxylic acid/aldehyde products respectively. Both reactions can be performed on preparative scale with isolated yields up to 80 %, and the epoxidations proceed with excellent enantioselectivity (>99 % ee). The divergent reactions can also be used to transform E/Z mixtures of allylic alcohols, enabling both product series to be isolated from a single reaction. The utility of the epoxidation method is exemplified in the total synthesis of both enantiomers of the insect pheromone disparlure, including a highly enantioselective gram-scale transformation. These reactions provide further evidence for the potential of UPOs as catalysts for the scalable preparation of important oxygenated intermediates.
非特异性过氧酶（UPOs）仅使用过氧化氢作为外部氧化剂催化有机底物的选择性氧化。来自泡盛曲霉的UPO的PaDa-I变体以互补的选择性催化Z-和E-烯丙醇的氧化，分别生成环氧化物和羧酸/醛产物。这两种反应都可以在制备规模上进行，分离产率高达80%，并且环氧化反应具有优异的对映选择性（>99% ee）。这种不同的反应还可用于转化烯丙醇的E/Z混合物，使得两个产物系列都能从单一反应中分离出来。环氧化方法的实用性在昆虫信息素 disparlure 两种对映体的全合成中得到了例证，包括一个高对映选择性的克级转化。这些反应进一步证明了UPOs作为可扩展制备重要氧化中间体催化剂的潜力。
