Coordinated Isonitriles

Vogler, Arnd

doi:10.1016/b978-0-12-706150-4.50015-0

Cited by 17 publications

(10 citation statements)

References 36 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Isocyanides have long been recognized for their ability to form complexes with various transition metals ( 28 ). However, the effects of extra- and intracellular transition metal availability on the production of these compounds have not been explored.…”

Section: Resultsmentioning

confidence: 99%

Fungal Isocyanide Synthases and Xanthocillin Biosynthesis in Aspergillus fumigatus

Lim

Won

Raffa

et al. 2018

mBio

View full text Add to dashboard Cite

Microbial secondary metabolites, including isocyanide moieties, have been extensively mined for their repertoire of bioactive properties. Although the first naturally occurring isocyanide (xanthocillin) was isolated from the fungus Penicillium notatum over half a century ago, the biosynthetic origins of fungal isocyanides remain unknown. Here we report the identification of a family of isocyanide synthases (ICSs) from the opportunistic human pathogen Aspergillus fumigatus. Comparative metabolomics of overexpression or knockout mutants of ICS candidate genes led to the discovery of a fungal biosynthetic gene cluster (BGC) that produces xanthocillin (xan). Detailed analysis of xanthocillin biosynthesis in A. fumigatus revealed several previously undescribed compounds produced by the xan BGC, including two novel members of the melanocin family of compounds. We found both the xan BGC and a second ICS-containing cluster, named the copper-responsive metabolite (crm) BGC, to be transcriptionally responsive to external copper levels and further demonstrated that production of metabolites from the xan BGC is increased during copper starvation. The crm BGC includes a novel type of fungus-specific ICS-nonribosomal peptide synthase (NRPS) hybrid enzyme, CrmA. This family of ICS-NRPS hybrid enzymes is highly enriched in fungal pathogens of humans, insects, and plants. Phylogenetic assessment of all ICSs spanning the tree of life shows not only high prevalence throughout the fungal kingdom but also distribution in species not previously known to harbor BGCs, indicating an untapped resource of fungal secondary metabolism.

show abstract

Section: Resultsmentioning

confidence: 99%

Fungal Isocyanide Synthases and Xanthocillin Biosynthesis in Aspergillus fumigatus

Lim

Won

Raffa

et al. 2018

mBio

View full text Add to dashboard Cite

show abstract

“…15 • from the quasi-linear geometry found in 1. The origin of this effect is certainly the backbonding from Ru to C1, 27 although concomitant rehybridization at N1 must be minimal as the bond distances of the N-isocyanide group in 2 do not change significantly compared to 1, i.e. the C1-N1 linkage remains a triple bond.…”

Section: The Terminal C Atom Of 1 Can Be Transferred: Mesityl Nitrilementioning

confidence: 99%

An exploding N-isocyanide reagent formally composed of anthracene, dinitrogen and a carbon atom

et al. 2017

View full text Add to dashboard Cite

Targeted as an example of a compound composed of a carbon atom together with two stable neutral leaving groups, 7-isocyano-7-azadibenzonorbornadiene, CNA (1, A = CH or anthracene) has been synthesized and spectroscopically and structurally characterized. The terminal C atom of 1 can be transferred: mesityl nitrile oxide reacts with 1 to produce carbon monoxide, likely via intermediacy of the N-isocyanate OCNA. Reaction of 1 with [RuCl(CO)(PCy)] leads to [RuCl(CO)(1)(PCy)] which decomposes unselectively: in the product mixture, the carbide complex [RuCl(C)(PCy)] was detected. Upon heating in the solid state or in solution, 1 decomposes to A, N and cyanogen (CN) as substantiated using molecular beam mass spectrometry, IR and NMR spectroscopy techniques.

show abstract

“…As isolobal analogues of carbon monoxide, organic isocyanides are well-suited for binding low-valent transition metals, including the constituent Fe atoms of our preferred electroactive subunit. 14 Ligands bearing multiple isocyanide moieties—some quite exotic—have previously been used to prepare extended coordination polymers, supramolecular assemblies, molecular wires, and three-dimensional framework materials. 15 For the purposes of this study, electroactive Fe 2 (PPh 2 ) 2 (CO) 5 fragments were appended to three very simple aromatic ligands bearing n isocyanide moieties: 2,6-dimethylphenyl isocyanide ( 2a , n = 1), 1,4-phenylene diisocyanide ( 2b , n = 2), and 2,4,6-triisocyanomesitylene ( 2c , n = 3).…”

Section: Resultsmentioning

confidence: 99%

“…The second step of our synthetic strategy emphasized the identification of organic “tethers” suitable for binding multiple subunits of 1 , thereby expanding the electron-sink capacity of the resulting covalent assembly. As isolobal analogues of carbon monoxide, organic isocyanides are well-suited for binding low-valent transition metals, including the constituent Fe atoms of our preferred electroactive subunit . Ligands bearing multiple isocyanide moietiessome quite exotichave previously been used to prepare extended coordination polymers, supramolecular assemblies, molecular wires, and three-dimensional framework materials .…”

Section: Resultsmentioning

confidence: 99%

A Modular Strategy for Expanding Electron-Sink Capacity in Noncanonical Cluster Assemblies

et al. 2021

View full text Add to dashboard Cite

A modular synthetic strategy is described whereby organometallic complexes exhibiting considerable electron-sink capacity may be assembled by using only a few simple molecular components. The Fe 2 (PPh 2 ) 2 (CO) 5 fragment was selected as a common electroactive component and was assembled around aromatic cores bearing one, two, or three isocyanide functional groups, with the resultant complexes possessing electron-sink capacities of two, four, and six electrons, respectively. The latter complex is noteworthy in that its electron-sink capacity was found to rival that of large multinuclear clusters (e.g., [Ni 32 C 6 (CO) 36 ] 6– and [Ni 38 Pt 6 (CO) 48 ] 6– ), which are often considered as benchmarks of electron-sink behavior. Moreover, the modular assembly bearing three Fe 2 (PPh 2 ) 2 (CO) 5 fragments was observed to undergo reduction to a hexaanionic state over a potential window of about −1.4 to −2.1 V (vs Fc/Fc + ), the relatively compressed range being attributed to potential inversions operative during the addition of the second, fourth, and sixth electrons. Such complexes may be designated noncanonical clusters because they exhibit redox properties similar to those of large multinuclear clusters yet lack the extensive network of metal–metal bonds and the condensed metallic cores that typify the latter.

show abstract

Coordinated Isonitriles

Cited by 17 publications

References 36 publications

Fungal Isocyanide Synthases and Xanthocillin Biosynthesis in Aspergillus fumigatus

Fungal Isocyanide Synthases and Xanthocillin Biosynthesis in Aspergillus fumigatus

An exploding N-isocyanide reagent formally composed of anthracene, dinitrogen and a carbon atom

A Modular Strategy for Expanding Electron-Sink Capacity in Noncanonical Cluster Assemblies

Contact Info

Product

Resources

About