Aerobic C−N Bond Formation through Enzymatic Nitroso-Ene-Type Reactions

No Thumbnail Available

Access rights

openAccess

URL

Journal Title

Journal ISSN

Volume Title

A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä

Date

2023-02-06

Major/Subject

Mcode

Degree programme

Language

en

Pages

Series

Angewandte Chemie - International Edition, articlenumber e202213671

Abstract

The biocatalytic oxidation of acylated hydroxylamines enables the direct and selective introduction of nitrogen functionalities by activation of allylic C−H bonds. Utilizing either laccases or an oxidase/peroxidase couple for the formal dehydrogenation of N-hydroxycarbamates and hydroxamic acids with air as the terminal oxidant, acylnitroso species are generated under particularly mild aqueous conditions. The reactive intermediates undergo C−N bond formation through an ene-type mechanism and provide high yields both in intramolecular and intermolecular enzymatic aminations. Investigations on different pathways of the two biocatalytic systems and labelling studies provide more insight into this unprecedented promiscuity of classical oxidoreductases as catalysts for nitroso-based transformations.

Description

| openaire: EC/H2020/865885/EU//ABIONYS Funding Information: We gratefully acknowledge financial support by the European Research Council (ABIONYS, 865885), the Academy of Finland (298250 & 324976), and the Ruth & Nils‐Erik Stenbäcks Stiftelse. C.J. thanks the Aalto School of Chemical Technology, as well as the Finnish Foundation for Technology Promotion and the Orion Research Foundation for personal grants. Publisher Copyright: © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

Keywords

Amination, Biocatalysis, Cyclization, Ene Reaction, Heterocycles

Other note

Citation

Jäger, C, Haase, M, Koschorreck, K, Urlacher, V B & Deska, J 2023, ' Aerobic C−N Bond Formation through Enzymatic Nitroso-Ene-Type Reactions ', Angewandte Chemie - International Edition, vol. 62, no. 7, e202213671 . https://doi.org/10.1002/anie.202213671