Grogan, Gideon James orcid.org/0000-0003-1383-7056, Li, Jason, Duran, Cristina et al. (4 more authors) (2024) Divergent Oxidation Reactions of E- and Z-Allylic Primary Alcohols by an Unspecific Peroxygenase. Angewandte Chemie International Edition. e202422241. ISSN 1433-7851
Abstract
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.
Metadata
Item Type: | Article |
---|---|
Authors/Creators: |
|
Dates: |
|
Institution: | The University of York |
Academic Units: | The University of York > Faculty of Sciences (York) > Chemistry (York) |
Funding Information: | Funder Grant number EPSRC EP/X014886/1 |
Depositing User: | Pure (York) |
Date Deposited: | 16 Dec 2024 15:30 |
Last Modified: | 23 Jan 2025 00:36 |
Published Version: | https://doi.org/10.1002/anie.202422241 |
Status: | Published online |
Refereed: | Yes |
Identification Number: | 10.1002/anie.202422241 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:220902 |