Issue 17, 2021

Halogenases: a palette of emerging opportunities for synthetic biology–synthetic chemistry and C–H functionalisation

Abstract

The enzymatic generation of carbon–halogen bonds is a powerful strategy used by both nature and synthetic chemists to tune the bioactivity, bioavailability and reactivity of compounds, opening up the opportunity for selective C–H functionalisation. Genes encoding halogenase enzymes have recently been shown to transcend all kingdoms of life. These enzymes install halogen atoms into aromatic and less activated aliphatic substrates, achieving selectivities that are often challenging to accomplish using synthetic methodologies. Significant advances in both halogenase discovery and engineering have provided a toolbox of enzymes, enabling the ready use of these catalysts in biotransformations, synthetic biology, and in combination with chemical catalysis to enable late stage C–H functionalisation. With a focus on substrate scope, this review outlines the mechanisms employed by the major classes of halogenases, while in parallel, it highlights key advances in the utilisation of the combination of enzymatic halogenation and chemical catalysis for C–H activation and diversification.

Graphical abstract: Halogenases: a palette of emerging opportunities for synthetic biology–synthetic chemistry and C–H functionalisation

Article information

Article type
Review Article
Submitted
14 Dec 2020
First published
09 Aug 2021
This article is Open Access
Creative Commons BY license

Chem. Soc. Rev., 2021,50, 9443-9481

Halogenases: a palette of emerging opportunities for synthetic biology–synthetic chemistry and C–H functionalisation

C. Crowe, S. Molyneux, S. V. Sharma, Y. Zhang, D. S. Gkotsi, H. Connaris and R. J. M. Goss, Chem. Soc. Rev., 2021, 50, 9443 DOI: 10.1039/D0CS01551B

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