Biochemistry: Biosynthesis of an organofluorine molecule

  title={Biochemistry: Biosynthesis of an organofluorine molecule},
  author={David O'Hagan and Christoph Schaffrath and Steven L. Cobb and John T. G. Hamilton and Cormac D. Murphy},
Although fluorine in the form of fluoride minerals is the most abundant halogen in the Earth's crust, only 12 naturally occurring organofluorine compounds have so far been found, and how these are biosynthesized remains a mystery. Here we describe an enzymatic reaction that occurs in the bacterium Streptomyces cattleya and which catalyses the conversion of fluoride ion and S-adenosylmethionine (SAM) to 5′-fluoro-5′-deoxyfluoroadenosine (5′-FDA). To our knowledge, this is the first fluorinase… 
This review summarizes the principal studies on biochemical and genetic aspects of the metabolism of organofluorine compounds (organoFs) in plants to form this rare class of fluorinated natural products.
Organo-Halogens and their Possible Involvement in Prebiotic Chemistry
In this review, we examined the possibility that some halogenated organic derivatives were used in the primitive ocean at the beginning of life on Earth. Firstly, we described the existence of
Biological fluorination from the sea: discovery of a SAM-dependent nucleophilic fluorinating enzyme from the marine-derived bacterium Streptomyces xinghaiensis NRRL B24674
A fluorinating enzyme from marine-derived Streptomyces xinghaiensis is discovered and characterised, which is ‘the most efficient’ fluorinase by far and, impressively, highly robust.
Biodegradation and biotransformation of organofluorine compounds
  • C. Murphy
  • Biology, Chemistry
    Biotechnology Letters
  • 2009
Here the current understanding of organofluorine catabolism in microorganisms is summarised.
What's new in enzymatic halogenations.
Crystal structure and mechanism of a bacterial fluorinating enzyme
The sequence and three-dimensional structure of the first native fluorination enzyme, 5′-fluoro-5′-deoxyadenosine synthase, from Streptomyces cattleya is reported, and a nucleophilic substitution mechanism for this biological fluorination reaction is proposed.
A Nonconventional Archaeal Fluorinase Identified by In Silico Mining for Enhanced Fluorine Biocatalysis
This work isolated and characterized putative fluorinases retrieved from systematic in silico mining and identified a nonconventional archaeal enzyme from Methanosaeta sp.
Defluorination of 4-fluorothreonine by threonine deaminase.
Among these three enzymes, threonine deaminase was found to catalyse a defluorination reaction to generate 4-hydroxy-α-ketobutyrate, which is supposed to be further metabolised by an aldolase that likely is a unique occurrence in the 4-FT-producing strains.
Enzyme-catalyzed C–F bond formation and cleavage
This review presents recent progress on enzyme-catalyzed C–F bond formation and cleavage, focused on describing C–f bond formation enabled by fluorinase and C-F bond cleavage catalyzed by oxidase, reductase, deaminase, and dehalogenase.
The fluorinase, the chlorinase and the duf-62 enzymes.


Isolation of an Aldehyde Dehydrogenase Involved in the Oxidation of Fluoroacetaldehyde to Fluoroacetate inStreptomyces cattleya
This is the first enzyme to be identified that is directly involved in fluorometabolite biosynthesis, and it has a high affinity for fluoroacetaldehyde and glycoaldehyde, but not acetaldehyde.
Fluoroacetaldehyde: a precursor of both fluoroacetateand 4-fluorothreonine in Streptomyces cattleya
Fluoroacetaldehyde is converted to fluoroacetate and 4-fluorothreonine in Streptomyces cattleya indicating that it is the biosynthetic precursor of both of these secondary metabolites.
Summary The tissues of numerous species of toxic plants from Africa, Australia and South America have been analysed for organic and inorganic fluorine. The presence of organically combined fluorine
Observations on the Metabolism of Fluoride in Acacia georginae and Some Other Plants
Experiments have been described which have led to believe that plants can convert fluoride, possibly in part, to a volatile form.
The base-sugar conformation of certain derivatives of adenosine
Base-sugar conformations of a range of adenosine derivatives have been confirmed by n.m.r. and c.d. measurements. The implications of the conformations for certain chemical properties, such as the
The diversity of naturally occurring organobromine compounds
Of the nearly 3200 known naturally occurring organohalogen compounds, more than 1600 contain bromine. These organobromines, which range in structural intricacy from the simple but enormously abundant
Biosynthesis of fluorothreonine and fluoroacetic acid by the thienamycin producer, Streptomyces cattleya.
19F NMR has provided evidence that the organism synthesizes fluoroacetate under the same fermentation conditions and the in vitro antibacterial spectrum of 4-fluorothreonine is presented.
The fluorinated natural products.