Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

NHC-Stabilized Iridium Nanoparticles as Catalysts in Hydrogen Isotope Exchange Reactions of Anilines.

ABSTRACT: The preparation of N-heterocyclic carbene-stabilized iridium nanoparticles and their application in hydrogen isotope exchange reactions is reported. These air-stable and easy-to-handle iridium nanoparticles showed a unique catalytic activity, allowing selective and efficient hydrogen isotope incorporation on anilines using D2 or T2 as isotopic source. The usefulness of this transformation has been demonstrated by the deuterium and tritium labeling of diverse complex pharmaceuticals.

SUBMITTER: Valero M

PROVIDER: S-EPMC7079112 | biostudies-literature | 2020 Feb

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

NHC-Stabilized Iridium Nanoparticles as Catalysts in Hydrogen Isotope Exchange Reactions of Anilines.

Valero Mégane M Bouzouita Donia D Palazzolo Alberto A Atzrodt Jens J Dugave Christophe C Tricard Simon S Feuillastre Sophie S Pieters Grégory G Chaudret Bruno B Derdau Volker V

Angewandte Chemie (International ed. in English) 20200129 9

The preparation of N-heterocyclic carbene-stabilized iridium nanoparticles and their application in hydrogen isotope exchange reactions is reported. These air-stable and easy-to-handle iridium nanoparticles showed a unique catalytic activity, allowing selective and efficient hydrogen isotope incorporation on anilines using D2 or T2 as isotopic source. The usefulness of this transformation has been demonstrated by the deuterium and tritium labeling of diverse complex pharmac ...[more]

PMID: 31849160

Similar Datasets

Comparison of Iridium(I) Catalysts in Temperature Mediated Hydrogen Isotope Exchange Reactions.

Project description:The reactivity and selectivity of iridium(I) catalysed hydrogen isotope exchange (HIE) reactions can be varied by using wide range of reaction temperatures. Herein, we have done a detailed comparison study with common iridium(I) catalysts (1-6) which will help us to understand and optimize the approaches of either high selectivity or maximum deuterium incorporation. We have demonstrated that the temperature window for these studied iridium(I) catalysts is surprisingly very broad. This principle was further proven in some HIE reactions on complex drug molecules.

| S-EPMC6718078 | biostudies-literature

Highly Selective Directed Iridium-Catalyzed Hydrogen Isotope Exchange Reactions of Aliphatic Amides.

Project description:For the first time, we describe highly selective homogeneous iridium-catalyzed hydrogen isotope exchange (HIE) of unactivated C(sp3 ) centers in aliphatic amides. When using the commercially available Kerr catalyst, the HIE with a series of common antibody-drug conjugate (ADC) linker side chains proceeds with high yields, high regioselectivity, and with deuterium incorporation up to 99 %. The method is fully translatable to the specific requirements of tritium chemistry and its effectiveness was demonstrated by direct tritium labelling of a maytansinoid. The scope of the method can be extended to simple amino acids, with high HIE activity observed for glycine and alanine. In di- and tripeptides, a very interesting protecting-group-dependent tunable selectivity was observed. DFT calculations gave insight into the energies of the transition states, thereby explaining the observed selectivity and the influence of the amino acid protecting groups.

| S-EPMC6033151 | biostudies-literature

C-H Functionalization-Prediction of Selectivity in Iridium(I)-Catalyzed Hydrogen Isotope Exchange Competition Reactions.

Project description:An assessment of the C-H activation catalyst [(COD)Ir(IMes)(PPh3 )]PF6 (COD=1,5-cyclooctadiene, IMes=1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene) in the deuteration of phenyl rings containing different functional directing groups is divulged. Competition experiments have revealed a clear order of the directing groups in the hydrogen isotope exchange (HIE) with an iridium (I) catalyst. Through DFT calculations the iridium-substrate coordination complex has been identified to be the main trigger for reactivity and selectivity in the competition situation with two or more directing groups. We postulate that the competition concept found in this HIE reaction can be used to explain regioselectivities in other transition-metal-catalyzed functionalization reactions of complex drug-type molecules as long as a C-H activation mechanism is involved.

| S-EPMC7232431 | biostudies-literature

Computationally-Guided Development of a Chelated NHC-P Iridium(I) Complex for the Directed Hydrogen Isotope Exchange of Aryl Sulfones.

Project description:Herein, we report the rational, computationally-guided design of an iridium(I) catalyst system capable of enabling directed hydrogen isotope exchange (HIE) with the challenging sulfone directing group. Substrate binding energy was used as a parameter to guide rational ligand design via an in silico catalyst screen, resulting in a lead series of chelated iridium(I) NHC-phosphine complexes. Subsequent preparative studies show that the optimal catalyst system displays high levels of activity in HIE, and we demonstrate the labeling of a broad scope of substituted aryl sulfones. We also show that the activity of the catalyst is maintained at low pressures of deuterium gas and apply these conditions to tritium radiolabeling, including the expedient synthesis of a tritium-labeled drug molecule.

| S-EPMC7587147 | biostudies-literature

Metathesis Reactions of a NHC-Stabilized Phosphaborene.

Project description:The BP unsaturated unit is a very attractive functional group as it provides novel reactivity and unique physical properties. Nonetheless, applications remain limited so far due to the bulky nature of B/P-protecting groups, required to prevent oligomerization. Herein, we report the synthesis and isolation of a N-heterocyclic carbene (NHC)-stabilized phosphaborene, bearing a trimethylsilyl (TMS) functionality at the P-terminal, as a room-temperature-stable crystalline solid accessible via facile NHC-induced trimethylsilyl chloride (TMSCl) elimination from its phosphinoborane precursor. This phosphaborene compound, bearing a genuine B=P bond, exhibits a remarkable ability for undergoing P-centre metathesis reactions, which allows the isolation of a series of unprecedented phosphaborenes. X-ray crystallographic analysis, UV/Vis spectroscopy, and DFT calculations provide insights into the B=P bonding situation.

| S-EPMC9401048 | biostudies-literature

NHC stabilized copper nanoparticles via reduction of a copper NHC complex.

Project description:The bottom-up synthesis of plasmonic NHC@CuNPs from common starting reagents, via the formation of the synthetically accessible NHC-Cu(I)-Br complex and its reduction by NH3·BH3 is reported. The resulting NHC@CuNPs have been characterized in detail by XPS, TEM and NMR spectroscopy. The stability of NHC@CuNPs was investigated under both inert and ambient conditions using UV-Vis analysis. While the NHC@CuNPs are stable under inert conditions for an extended period of time, the NPs oxidize under air to form CuxO with concomitant release of the stabilizing NHC ligand.

| S-EPMC10408246 | biostudies-literature

Cationic NHC-Phosphine Iridium Complexes: Highly Active Catalysts for Base-Free Hydrogenation of Ketones.

Project description:Novel bidentate N-heterocyclic carbene-phosphine iridium complexes have been synthesized and evaluated in the hydrogenation of ketones. Reported catalytic systems require base additives and, if excluded, need elevated temperature or high pressure of hydrogen gas to achieve satisfactory reactivity. The developed catalysts showed extremely high reactivity and good enantioselectivity under base-free and mild conditions. In the presence of 1 mol % catalyst under 1 bar hydrogen pressure at room temperature, hydrogenation was complete in 30 minutes giving up to 96 % ee. Again, this high reactivity was achieved in additive-free conditions. Mechanistic experiments demonstrated that balloon pressure of hydrogen was sufficient to form the activate species by reducing and eliminating the 1,5-cyclooctadiene ligand. The pre-activated catalyst was able to hydrogenate acetophenone with 89 % conversion in 5 min.

| S-EPMC7693092 | biostudies-literature

The isotope-exchange reactions of ox heart phosphofructokinase.

Project description:1. Ox heart phosphofructokinase catalyses isotope-exchange reactions at pH6.7 between ADP and ATP, and between fructose 6-phosphate and fructose 1,6-diphosphate, the latter reaction being absolutely dependent on the presence of the magnesium complex of ADP. 2. The reaction kinetics are hyperbolic with respect to substrate concentration for both exchange reactions (within the experimental error). 3. The influence of pH, AMP and citrate suggests that the fructose 6-phosphate-fructose 1,6-diphosphate exchange is subject to effector control, and is abolished by dissociation of the enzyme. 4. These results are discussed in relation to the reaction mechanism of the enzyme.

| S-EPMC1176761 | biostudies-other

Hydrogen-borrowing and interrupted-hydrogen-borrowing reactions of ketones and methanol catalyzed by iridium.

Project description:Reported herein is the use of catalytic [{Ir(cod)Cl}2 ] to facilitate hydrogen-borrowing reactions of ketone enolates with methanol at 65?°C. An oxygen atmosphere accelerates the process, and when combined with the use of a bulky monodentate phosphine ligand, interrupts the catalytic cycle by preventing enone reduction. Subsequent addition of pro-nucleophiles to the reaction mixture allowed a one-pot methylenation/conjugate addition protocol to be developed, which greatly expands the range of products that can be made by this methodology.

| S-EPMC4344817 | biostudies-other

Iridium Cyclooctene Complex That Forms a Hyperpolarization Transfer Catalyst before Converting to a Binuclear C-H Bond Activation Product Responsible for Hydrogen Isotope Exchange.

Project description:[IrCl(COE)2]2 (1) reacts with pyridine (py) and H2 to form crystallographically characterized IrCl(H)2(COE)(py)2 (2). 2 undergoes py loss to form 16-electron IrCl(H)2(COE)(py) (3), with equivalent hydride ligands. When this reaction is studied with parahydrogen, 1 efficiently achieves hyperpolarization of free py (and nicotinamide, nicotine, 5-aminopyrimidine, and 3,5-lutudine) via signal amplification by reversible exchange (SABRE) and hence reflects a simple and readily available precatayst for this process. 2 reacts further over 48 h at 298 K to form crystallographically characterized (Cl)(H)(py)(μ-Cl)(μ-H)(κ-μ-NC5H4)Ir(H)(py)2 (4). This dimer is active in the hydrogen isotope exchange process that is used in radiopharmaceutical preparations. Furthermore, while [Ir(H)2(COE)(py)3]PF6 (6) forms upon the addition of AgPF6 to 2, its stability precludes its efficient involvement in SABRE.

| S-EPMC5193467 | 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