Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

A biocompatible alkene hydrogenation merges organic synthesis with microbial metabolism.

ABSTRACT: Organic chemists and metabolic engineers use orthogonal technologies to construct essential small molecules such as pharmaceuticals and commodity chemicals. While chemists have leveraged the unique capabilities of biological catalysts for small-molecule production, metabolic engineers have not likewise integrated reactions from organic synthesis with the metabolism of living organisms. Reported herein is a method for alkene hydrogenation which utilizes a palladium catalyst and hydrogen gas generated directly by a living microorganism. This biocompatible transformation, which requires both catalyst and microbe, and can be used on a preparative scale, represents a new strategy for chemical synthesis that combines organic chemistry and metabolic engineering.

SUBMITTER: Sirasani G

PROVIDER: S-EPMC4127630 | biostudies-literature | 2014 Jul

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

A biocompatible alkene hydrogenation merges organic synthesis with microbial metabolism.

Sirasani Gopal G Tong Liuchuan L Balskus Emily P EP

Angewandte Chemie (International ed. in English) 20140610 30

Organic chemists and metabolic engineers use orthogonal technologies to construct essential small molecules such as pharmaceuticals and commodity chemicals. While chemists have leveraged the unique capabilities of biological catalysts for small-molecule production, metabolic engineers have not likewise integrated reactions from organic synthesis with the metabolism of living organisms. Reported herein is a method for alkene hydrogenation which utilizes a palladium catalyst and hydrogen gas gener ...[more]

PMID: 24916924

Similar Datasets

Alkene Metalates as Hydrogenation Catalysts.

Project description:First-row transition-metal complexes hold great potential as catalysts for hydrogenations and related reductive reactions. Homo- and heteroleptic arene/alkene metalates(1-) (M=Co, Fe) are a structurally distinct catalyst class with good activities in hydrogenations of alkenes and alkynes. The first syntheses of the heteroleptic cobaltates [K([18]crown-6)][Co(η4 -cod)(η2 -styrene)2 ] (5) and [K([18]crown-6)][Co(η4 -dct)(η4 -cod)] (6), and the homoleptic complex [K(thf)2 ][Co(η4 -dct)2 ] (7; dct=dibenzo[a,e]cyclooctatetraene, cod=1,5-cyclooctadiene), are reported. For comparison, two cyclopentadienylferrates(1-) were synthesized according to literature procedures. The isolated and fully characterized monoanionic complexes were competent precatalysts in alkene hydrogenations under mild conditions (2 bar H2 , r.t., THF). Mechanistic studies by NMR spectroscopy, ESI mass spectrometry, and poisoning experiments documented the operation of a homogeneous mechanism, which was initiated by facile redox-neutral π-ligand exchange with the substrates followed by H2 activation. The substrate scope of the investigated precatalysts was also extended to polar substrates (ketones and imines).

| S-EPMC5861671 | biostudies-literature

Cobalt-catalyzed alkene hydrogenation by reductive turnover.

Project description:Earth abundant metal catalysts hold advantages in cost, environmental burden and chemoselectivity over precious metal catalysts. Differences in reactivity for a given metal center result from ligand field strength, which can promote reaction through either open- or closed-shell carbon intermediates. Herein we report a simple protocol for cobalt-catalyzed alkene reduction. Instead of using an oxidative turnover mechanism that requires stoichiometric hydride, we find a reductive turnover mechanism that requires stoichiometric proton. The reaction mechanism appears to involve coordination and hydrocobaltation of terminal alkenes.

| S-EPMC10573012 | biostudies-literature

Extraordinarily large kinetic isotope effect on alkene hydrogenation over Rh-based intermetallic compounds.

Project description:A series of Rh-based intermetallic compounds supported on silica was prepared and tested in alkene hydrogenation at room temperature. H2 and D2 were used as the hydrogen sources and the kinetic isotope effect (KIE) in hydrogenation was studied. In styrene hydrogenation, the KIE values differed strongly depending on the intermetallic phase, and some intermetallic compounds with Sb and Pb exhibited remarkably high KIE values (>28). An extraordinarily high KIE value of 91, which has never been reported in catalytic reactions at room temperature, was observed particularly for RhPb2/SiO2. RhPb2/SiO2 also showed high KIE values in the hydrogenation of other unsaturated hydrocarbons such as phenylacetylene and cyclohexene. The density functional theory calculation focused on the surface diffusion of hydrogen suggested no contribution of the quantum tunneling effect to the high KIE values observed. A kinetic study revealed that the dissociative adsorption of H2 (D2) was the rate-determining step in the styrene hydrogenation over RhPb2/SiO2. We propose that the large KIE originates from the quantum tunneling occurring at the hydrogen adsorption process with the aid of the specific surface structure of the intermetallic compound and adsorbate alkene.

| S-EPMC6711132 | biostudies-literature

Microbial Synthesis and Transformation of Inorganic and Organic Chlorine Compounds.

Project description:Organic and inorganic chlorine compounds are formed by a broad range of natural geochemical, photochemical and biological processes. In addition, chlorine compounds are produced in large quantities for industrial, agricultural and pharmaceutical purposes, which has led to widespread environmental pollution. Abiotic transformations and microbial metabolism of inorganic and organic chlorine compounds combined with human activities constitute the chlorine cycle on Earth. Naturally occurring organochlorines compounds are synthesized and transformed by diverse groups of (micro)organisms in the presence or absence of oxygen. In turn, anthropogenic chlorine contaminants may be degraded under natural or stimulated conditions. Here, we review phylogeny, biochemistry and ecology of microorganisms mediating chlorination and dechlorination processes. In addition, the co-occurrence and potential interdependency of catabolic and anabolic transformations of natural and synthetic chlorine compounds are discussed for selected microorganisms and particular ecosystems.

| S-EPMC6299022 | biostudies-other

An Air-Stable Alkene-Derived Organic Radical Cation.

Project description:Alkenes are known to undergo oxidation to radical cations and dications. The radical cations are often highly reactive and not stable under air. Herein, we report the synthesis, isolation, characterization, and molecular structure of an alkene-derived radical cation A, which is stable in air both in the solid state and in solution. The access to this compound was facilitated from E-diamino tri-substituted alkene B as a synthon for the synthesis of A through one-electron oxidation. The E-diamino tri-substituted alkene B was synthesized by the two-electron reduction of N,N'-1,2-propylene-bridged bis-2-phenyl-pyrrolinium cation C. Under two-electron oxidation, alkene B transforms back to cation C involving a double carbocation rearrangement.

| S-EPMC8757455 | biostudies-literature

Microbial metabolism: optimal control of uptake versus synthesis.

Project description:Microbes require several complex organic molecules for growth. A species may obtain a required factor by taking up molecules released by other species or by synthesizing the molecule. The patterns of uptake and synthesis set a flow of resources through the multiple species that create a microbial community. This article analyzes a simple mathematical model of the tradeoff between uptake and synthesis. Key factors include the influx rate from external sources relative to the outflux rate, the rate of internal decay within cells, and the cost of synthesis. Aspects of demography also matter, such as cellular birth and death rates, the expected time course of a local resource flow, and the associated lifespan of the local population. Spatial patterns of genetic variability and differentiation between populations may also strongly influence the evolution of metabolic regulatory controls of individual species and thus the structuring of microbial communities. The widespread use of optimality approaches in recent work on microbial metabolism has ignored demography and genetic structure.

| S-EPMC3940620 | biostudies-literature

The environmental fate of organic pollutants through the global microbial metabolism.

Project description:The production of new chemicals for industrial or therapeutic applications exceeds our ability to generate experimental data on their biological fate once they are released into the environment. Typically, mixtures of organic pollutants are freed into a variety of sites inhabited by diverse microorganisms, which structure complex multispecies metabolic networks. A machine learning approach has been instrumental to expose a correlation between the frequency of 149 atomic triads (chemotopes) common in organo-chemical compounds and the global capacity of microorganisms to metabolise them. Depending on the type of environmental fate defined, the system can correctly predict the biodegradative outcome for 73-87% of compounds. This system is available to the community as a web server (http://www.pdg.cnb.uam.es/BDPSERVER). The application of this predictive tool to chemical species released into the environment provides an early instrument for tentatively classifying the compounds as biodegradable or recalcitrant. Automated surveys of lists of industrial chemicals currently employed in large quantities revealed that herbicides are the group of functional molecules more difficult to recycle into the biosphere through the inclusive microbial metabolism.

| S-EPMC1911198 | biostudies-other

Ultraflexible organic amplifier with biocompatible gel electrodes.

Project description:In vivo electronic monitoring systems are promising technology to obtain biosignals with high spatiotemporal resolution and sensitivity. Here we demonstrate the fabrication of a biocompatible highly conductive gel composite comprising multi-walled carbon nanotube-dispersed sheet with an aqueous hydrogel. This gel composite exhibits admittance of 100 mS cm(-2) and maintains high admittance even in a low-frequency range. On implantation into a living hypodermal tissue for 4 weeks, it showed a small foreign-body reaction compared with widely used metal electrodes. Capitalizing on the multi-functional gel composite, we fabricated an ultrathin and mechanically flexible organic active matrix amplifier on a 1.2-?m-thick polyethylene-naphthalate film to amplify (amplification factor: ?200) weak biosignals. The composite was integrated to the amplifier to realize a direct lead epicardial electrocardiography that is easily spread over an uneven heart tissue.

| S-EPMC5411732 | biostudies-literature

Alkene hydrogenation activity of enoate reductases for an environmentally benign biosynthesis of adipic acid.

Project description:Adipic acid, a precursor for Nylon-6,6 polymer, is one of the most important commodity chemicals, which is currently produced from petroleum. The biosynthesis of adipic acid from glucose still remains challenging due to the absence of biocatalysts required for the hydrogenation of unsaturated six-carbon dicarboxylic acids to adipic acid. Here, we demonstrate the first enzymatic hydrogenation of 2-hexenedioic acid and muconic acid to adipic acid using enoate reductases (ERs). ERs can hydrogenate 2-hexenedioic acid and muconic acid producing adipic acid with a high conversion rate and yield in vivo and in vitro. Purified ERs exhibit a broad substrate spectrum including aromatic and aliphatic 2-enoates and a significant oxygen tolerance. The discovery of the hydrogenation activity of ERs contributes to an understanding of the catalytic mechanism of these poorly characterized enzymes and enables the environmentally benign biosynthesis of adipic acid and other chemicals from renewable resources.

| S-EPMC5460604 | biostudies-literature

Ligand Substitution and Electronic Structure Studies of Bis(phosphine)Cobalt Cyclooctadiene Precatalysts for Alkene Hydrogenation.

Project description:Diene self-exchange reactions of the 17-electron, formally cobalt(0) cyclooctadienyl precatalyst, (R,R)-(iPrDuPhos)Co(COD) (P 2 CoCOD, (R,R)-iPrDuPhos = 1,2-bis((2R,5R)-2,5-diisopropylphospholano)benzene, COD = 1,5-cyclooctadiene) were studied using natural abundance and deuterated 1,5-cyclooctadiene. Exchange of free and coordinated diene was observed at ambient temperature in benzene-d 6 solution and kinetic studies support a dissociative process. Both neutral P 2 CoCOD and the 16-electron, cationic cobalt(I) complex, [(R,R)-(iPrDuPhos)Co(COD)][BArF 4] (BArF 4 = B[(3,5-(CF3)2)C6H3]4) underwent instantaneous displacement of the 1,5-cyclooctadiene ligand by carbon monoxide and generated the corresponding carbonyl derivatives. The solid-state parameters, DFT-computed Mulliken spin density and analysis of molecular orbitals suggest an alternative description of P 2 CoCOD as low-spin cobalt(II) with the 1,5-cyclooctadiene acting as a LX2-type ligand. This view of the electronic structure provides insight into the nature of the ligand substitution processes and the remarkable stability of the neutral cobalt complexes toward protic solvents observed during catalytic alkene hydrogenation.

| S-EPMC8317443 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data