Enzymatic halogenation and dehalogenation reactions: Pervasive and mechanistically diverse

TitleEnzymatic halogenation and dehalogenation reactions: Pervasive and mechanistically diverse
Publication TypeJournal Article
Year of Publication2017
AuthorsAgarwal V., Miles Z.D, Winter J.M, Eustaquio A.S, Gamal A.AEl, Moore BS
JournalChemical Reviews
Volume117
Pagination5619-5674
Date Published2017/04
Type of ArticleReview
ISBN Number0009-2665
Accession NumberWOS:000400321700009
Keywordsadenosyl-l-methionine; antitumor antibiotic c-1027; biosynthetic gene-cluster; cis-3-chloroacrylic acid dehalogenase; curvularia-inaequalis; flavin-dependent halogenase; fungus; halogenase; marine natural-products; nonheme iron; site-directed mutagenesis; tryptophan 7-halogenase prna
Abstract

Naturally produced halogenated compounds are ubiquitous across all domains of life where they perform a multitude of biological functions and adopt a diversity of chemical structures. Accordingly, a diverse collection of enzyme catalysts to install and remove halogens from organic scaffolds has evolved in nature. Accounting for the different chemical properties of the four halogen atoms (fluorine, chlorine, bromine, and iodine) and the diversity and chemical reactivity of their organic substrates, enzymes performing biosynthetic and degradative halogenation chemistry utilize numerous mechanistic strategies involving oxidation, reduction, and substitution. Biosynthetic halogenation reactions range from simple aromatic substitutions to stereoselective C-H functionalizations on remote carbon centers and can initiate the formation of simple to complex ring structures. Dehalogenating enzymes, on the other hand, are best known for removing halogen atoms from man-made organohalogens, yet also function naturally, albeit rarely, in metabolic pathways. This review details the scope and mechanism of nature's halogenation and dehalogenation enzymatic strategies, highlights gaps in our understanding, and posits where new advances in the field might arise in the near future.

DOI10.1021/acs.chemrev.6b00571
Short TitleChem. Rev.
Student Publication: 
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