Marine isocyanides and related natural products ? structure, biosynthesis and ecology

Garson, Mary J.; Simpson, Jamie S.

doi:10.1039/b302359c

Cited by 161 publications

(134 citation statements)

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“…Since then more than 150 isocyano terpenes have been structurally characterized; these are predominantly sesquiterpenes and diterpenes with at least one nitrogen that forms a cyanide functional group. The diversity of marine isocyano terpene structures has been reviewed (Edenborough and Herbert, 1988;Chang and Scheuer, 1993;Chang, 2000;Garson and Simpson, 2004), and here we briefly also discuss the structurally related isothiocyanates and formamides. Isocyano terpenes are found in a variety of organisms, including fungi, bacteria, cyanobacteria, sponges, and nudibranchs; however, for the purpose of this review, we focus on the compounds isolated from marine sponges and nudibranchs.…”

Section: Isocyano Terpenesmentioning

confidence: 99%

“…During the last 20 years, multiple reviews of the biosynthesis of isocyano terpenes and related compounds have been published (Edenborough and Herbert, 1988;Scheuer, 1992;Garson and Simpson, 2004). Because of their structural similarity to tyrosine, most terrestrial isocyano terpenes are thought to be derived from amino acids; however, the marine isocyano terpenes are not structurally similar to amino acids, suggesting a different biosynthetic pathway.…”

Section: Isocyano Terpenesmentioning

confidence: 99%

“…Further studies on the biosynthesis of isocyanide compounds from inorganic cyanide precursors by the sponges Amphimedon terpenensis, Acanthella cavernosa, Axinyssa n. sp., and Stylotella aurantium are reviewed by Garson and Simpson (2004).…”

Section: Isocyano Terpenesmentioning

confidence: 99%

See 2 more Smart Citations

Chemical Defenses: From Compounds to Communities

Paul

Arthur

Ritson‐Williams

et al. 2007

The Biological Bulletin

180

152

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Section: Isocyano Terpenesmentioning

confidence: 99%

Section: Isocyano Terpenesmentioning

confidence: 99%

See 1 more Smart Citation

Chemical Defenses: From Compounds to Communities

Paul

Arthur

Ritson‐Williams

et al. 2007

The Biological Bulletin

180

152

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“…Isonitriles as well as nitriles are generally highly toxic and produced in nature by various organisms, including bacteria, fungi, marine sponges, etc. (15)(16)(17). An isocyanide metabolite, xanthocillin, was first isolated from Penicillium notatum (18).…”

mentioning

confidence: 99%

Amine-synthesizing enzyme N-substituted formamide deformylase: Screening, purification, characterization, and gene cloning

Fukatsu

Hashimoto²,

Goda³

et al. 2004

Proc. Natl. Acad. Sci. U.S.A.

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N-substituted formamide was produced through the hydration of an isonitrile by isonitrile hydratase in the isonitrile metabolism. The former compound was further degraded by a microorganism, strain F164, which was isolated from soil through an acclimatization culture. The N-substituted formamide-degrading microorganism was identified as Arthrobacter pascens. The microbial degradation was found to proceed through an enzymatic reaction, the N-substituted formamide being hydrolyzed to yield the corresponding amine and formate. The enzyme, designated as Nsubstituted formamide deformylase (NfdA), was purified and characterized. The native enzyme had a molecular mass of Ϸ61 kDa and consisted of two identical subunits. It stoichiometrically catalyzed the hydrolysis of N-benzylformamide (an N-substituted formamide) to benzylamine and formate. Of all of the N-substituted formamides tested, N-benzylformamide was the most suitable substrate for the enzyme. However, no amides were accepted as substrates. The gene (nfdA) encoding this enzyme was also cloned. The deduced amino acid sequence of nfdA exhibited the highest overall sequence identity (28%) with those of regulatory proteins among known proteins. Only the N-terminal region (residues 58 -72) of NfdA also showed significant sequence identity (27-73%) to that of each member of the amidohydrolase superfamily, although there was no similarity in the overall sequence except in the above limited region. N itriles are very toxic and generally unbiodegradable organic compounds containing a CϵN moiety. We have studied nitrile metabolism (1-3) and clarified the structures and functions of enzymes [i.e., nitrilase (4-7), nitrile hydratase (8-11), and amidase (12-14)] involved in metabolism and their genes and regulation mechanisms.On the other hand, information is quite limited on the metabolism of an isonitrile (more generally called an isocyanide) containing an isocyano group (ϪNϵC), which is an isomer of a nitrile. Isonitriles as well as nitriles are generally highly toxic and produced in nature by various organisms, including bacteria, fungi, marine sponges, etc. (15-17). An isocyanide metabolite, xanthocillin, was first isolated from Penicillium notatum (18). This isonitrile exhibits a wide antibiotic activity spectrum (19). Although parts of the metabolic intermediates of some isonitriles have been elucidated through incorporation experiments (20-24), their synthetic and degradative pathways remained entirely undetermined. Furthermore, to our knowledge none of the enzymes involved in isonitrile metabolism, except for the enzyme we describe below, has yet been identified.Recently, we isolated a microorganism, Pseudomonas putida strain N19-2, that is able to degrade isonitriles from soil and discovered an isonitrile-metabolizing enzyme, designated as isonitrile hydratase (EC 4.2.1.103), in this strain (25,26). This enzyme catalyzes the hydration of an isonitrile [R-NϵC] to the corresponding N-substituted formamide [R-NH-CH(ϭO)], and confers the ability of isonitrile-degrada...

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“…The isocyano group, which possesses an unusual valence structure and reactivity, exhibits a dual nucleophilic/electrophilic character, which is often exploited for synthetic applications, e.g., in the synthesis of peptides, coordination chemistry, organometallic reactions, and carbohydrate chemistry (5). On the other hand, many natural isonitriles have been isolated from various organisms, including bacteria, fungi, and marine sponges (5)(6)(7). An isocyanide metabolite, xanthocillin, was first isolated from Penicillium notatum (8).…”

mentioning

confidence: 99%

A New Synthetic Route to N -Benzyl Carboxamides through the Reverse Reaction of N -Substituted Formamide Deformylase

Hashimoto

Sakashita

Fukatsu

et al. 2014

Appl Environ Microbiol

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Here, we discovered that this enzyme catalyzed the reverse reaction, synthesizing N-benzylformamide (NBFA) from benzylamine and formate. The reverse reaction proceeded only in the presence of high substrate concentrations. The effects of pH and inhibitors on the reverse reaction were almost the same as those on the forward reaction, suggesting that the forward and reverse reactions are both catalyzed at the same catalytic site. Bisubstrate kinetic analysis using formate and benzylamine and dead-end inhibition studies using a benzylamine analogue, aniline, revealed that the reverse reaction of this enzyme proceeds via an ordered two-substrate, two-product (bi-bi) mechanism in which formate binds first to the enzyme active site, followed by benzylamine binding and the subsequent release of NBFA. To our knowledge, this is the first report of the reverse reaction of an amine-forming deformylase. Surprisingly, analysis of the substrate specificity for acids demonstrated that not only formate, but also acetate and propionate (namely, acids with numbers of carbon atoms ranging from C 1 to C 3 ), were active as acid substrates for the reverse reaction. Through this reaction, N-substituted carboxamides, such as NBFA, N-benzylacetamide, and N-benzylpropionamide, were synthesized from benzylamine and the corresponding acid substrates.

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Marine isocyanides and related natural products ? structure, biosynthesis and ecology

Cited by 161 publications

References 115 publications

Chemical Defenses: From Compounds to Communities

Chemical Defenses: From Compounds to Communities

Amine-synthesizing enzyme N-substituted formamide deformylase: Screening, purification, characterization, and gene cloning

A New Synthetic Route to N -Benzyl Carboxamides through the Reverse Reaction of N -Substituted Formamide Deformylase

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