Browse
Submit Data
Databases
API
Help

Dataset Information

43 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Photo-Induced Ruthenium-Catalyzed C-H Benzylations and Allylations at Room Temperature.

ABSTRACT: The ruthenium-catalyzed synthesis of diarylmethane compounds was realized under exceedingly mild photoredox conditions without the use of exogenous photocatalysts. The versatility and robustness of the ruthenium-catalyzed C-H benzylation was reflected by an ample scope, including multifold C-H functionalizations, as well as transformable pyrazoles, imidates and sensitive nucleosides. Mechanistic studies were indicative of a photoactive cyclometalated ruthenium complex, which also enabled versatile C-H allylations.

SUBMITTER: Struwe J

PROVIDER: S-EPMC9293244 | biostudies-literature | 2021 Nov

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Photo-Induced Ruthenium-Catalyzed C-H Benzylations and Allylations at Room Temperature.

Struwe Julia J Korvorapun Korkit K Zangarelli Agnese A Ackermann Lutz L

Chemistry (Weinheim an der Bergstrasse, Germany) 20211005 65

The ruthenium-catalyzed synthesis of diarylmethane compounds was realized under exceedingly mild photoredox conditions without the use of exogenous photocatalysts. The versatility and robustness of the ruthenium-catalyzed C-H benzylation was reflected by an ample scope, including multifold C-H functionalizations, as well as transformable pyrazoles, imidates and sensitive nucleosides. Mechanistic studies were indicative of a photoactive cyclometalated ruthenium complex, which also enabled versati ...[more]

PMID: 34435716

Similar Datasets

Photo-Induced Ruthenium-Catalyzed C-H Arylations at Ambient Temperature.

Project description:Ambient temperature ruthenium-catalyzed C-H arylations were accomplished by visible light without additional photocatalysts. The robustness of the ruthenium-catalyzed C-H functionalization protocol was reflected by a broad range of sensitive functional groups and synthetically useful pyrazoles, triazoles and sensitive nucleosides and nucleotides, as well as multifold C-H functionalizations. Biscyclometalated ruthenium complexes were identified as the key intermediates in the photoredox ruthenium catalysis by detailed computational and experimental mechanistic analysis. Calculations suggested that the in situ formed photoactive ruthenium species preferably underwent an inner-sphere electron transfer.

| S-EPMC7589283 | biostudies-literature

Room-temperature photo-induced martensitic transformation in a protein crystal.

Project description:Martensitic transformations are the first-order crystal-to-crystal phase transitions that occur mostly in materials such as steel, alloys and ceramics, thus having many technological applications. These phase transitions are rarely observed in molecular crystals and have not been detected in protein crystals. Reversibly switchable fluorescent proteins are widely used in biotechnology, including super-resolution molecular imaging, and hold promise as candidate biomaterials for future high-tech applications. Here, we report on a reversibly switchable fluorescent protein, Tetdron, whose crystals undergo a photo-induced martensitic transformation at room temperature. Room-temperature X-ray crystallography demonstrates that at equilibrium Tetdron chromophores are all in the trans configuration, with an ∼1:1 mixture of their protonated and deprotonated forms. Irradiation of a Tetdron crystal with 400 nm light induces a martensitic transformation, which results in Tetdron tetramerization at room temperature revealed by X-ray photocrystallography. Crystal and solution spectroscopic measurements provide evidence that the photo-induced martensitic phase transition is coupled with the chromophore deprotonation, but no trans-cis isomerization is detected in the structure of an irradiated crystal. It is hypothesized that protein dynamics assists in the light-induced proton transfer from the chromophore to the bulk solvent and in the ensuing martensitic phase transition. The unique properties of Tetdron may be useful in developing novel biomaterials for optogenetics, data storage and nanotechnology.

| S-EPMC6608640 | biostudies-literature

Photo-thermo-induced room-temperature phosphorescence through solid-state molecular motion.

Project description:The development of smart-responsive materials, in particular those with non-invasive, rapid responsive phosphorescence, is highly desirable but has rarely been described. Herein, we designed and prepared a series of molecular rotors containing a triazine core and three bromobiphenyl units: o-Br-TRZ, m-Br-TRZ, and p-Br-TRZ. The bromine and triazine moieties serve as room temperature phosphorescence-active units, and the bromobiphenyl units serve as rotors to drive intramolecular rotation. When irradiated with strong ultraviolet photoirradiation, intramolecular rotations of o-Br-TRZ, m-Br-TRZ, and p-Br-TRZ increase, successively resulting in a photothermal effect via molecular motions. Impressively, the photothermal temperature attained by p-Br-TRZ is as high as 102 °C, and synchronously triggers its phosphorescence due to the ordered molecular arrangement after molecular motion. The thermal effect is expected to be important for triggering efficient phosphorescence, and the photon input for providing a precise and non-invasive stimulus. Such sequential photo-thermo-phosphorescence conversion is anticipated to unlock a new stimulus-responsive phosphorescence material without chemicals invasion.

| S-EPMC9259671 | biostudies-literature

Ruthenium-catalyzed photo cross-linking of fibrin-based engineered tissue.

Project description:Most cross-linking methods utilize chemistry or physical processes that are detrimental to cells and tissue development. Those that are not as harmful often do not provide a level of strength that ultimately meets the required application. The purpose of this work was to investigate the use of a ruthenium-sodium persulfate cross-linking system to form dityrosine in fibrin-based engineered tissue. By utilizing the tyrosine residues inherent to fibrin and cell-deposited proteins, at least 3-fold mechanical strength increases and 10-fold stiffness increases were achieved after cross-linking. This strengthening and stiffening effect was found to increase with culture duration prior to cross-linking such that physiologically relevant properties were obtained. Fibrin was not required for this effect as demonstrated by testing with collagen-based engineered tissue. Cross-linked tissues were implanted subcutaneously and shown to have minimal inflammation after 30 days, similar to non-cross-linked controls. Overall, the method employed is rapid, non-toxic, minimally inflammatory, and is capable of increasing strength and stiffness of engineered tissues to physiological levels.

| S-EPMC3791330 | biostudies-literature

Selective Room-Temperature Hydrogenation of Amides to Amines and Alcohols Catalyzed by a Ruthenium Pincer Complex and Mechanistic Insight.

Project description:We report a room-temperature protocol for the hydrogenation of various amides to produce amines and alcohols. Compared with most previous reports for this transformation, which use high temperatures (typically, 100-200 °C) and H2 pressures (10-100 bar), this system proceeds under extremely mild conditions (RT, 5-10 bar of H2). The hydrogenation is catalyzed by well-defined ruthenium-PNNH pincer complexes (0.5 mol %) with potential dual modes of metal-ligand cooperation. An unusual Ru-amidate complex was formed and crystallographically characterized. Mechanistic investigations indicate that the room-temperature hydrogenation proceeds predominantly via the Ru-N amido/amine metal-ligand cooperation.

| S-EPMC7236134 | biostudies-literature

Asymmetric Ruthenium-Catalyzed Carbonyl Allylations by Gaseous Allene via Hydrogen Auto-Transfer: 1° vs 2° Alcohol Dehydrogenation for Streamlined Polyketide Construction.

Project description:Iodide-bound ruthenium-JOSIPHOS complexes catalyze the redox-neutral C-C coupling of primary alcohols 2a-2r with the gaseous allene (propadiene) 1a to form enantiomerically enriched homoallylic alcohols 3a-3r with complete atom-efficiency. Using formic acid as reductant, aldehydes dehydro-2a and dehydro-2c participate in reductive C-C coupling with allene to deliver adducts 3a and 3c with comparable levels of asymmetric induction. Deuterium labeling studies corroborate a mechanism in which alcohol dehydrogenation triggers allene hydroruthenation to form transient allylruthenium-aldehyde pairs that participate in carbonyl addition. Notably, due to a kinetic preference for primary alcohol dehydrogenation, chemoselective C-C coupling of 1°,2°-1,3-diols occurs in the absence of protecting groups. As illustrated by the synthesis of C7-C15 of spirastrellolide B and F (7 vs 17 steps), C3-C10 of cryptocarya diacetate (3 vs 7 or 9 steps), and a fragment common to C8'-C14' of mycolactone F (1 vs 4 steps) and C22-C28 marinomycin A (1 vs 9 steps), this capability streamlines type I polyketide construction.

| S-EPMC10586519 | biostudies-literature

Room-Temperature Synthesis of Thioether-Stabilized Ruthenium Nanocubes and Their Optical Properties.

Project description:Controlling the nucleation and growth processes for nanoparticle synthesis allows the development of well-defined structures that offer unique chemical and physical properties. Here, we report a wet chemical reduction method for synthesizing ruthenium nanocubes (Ru NCs) that display plasmonic properties at room temperature (RT). The growth of the particles to form nanostructured cubes was established by varying the carbon chain length of the thioether stabilizing ligands and the reaction time to produce stable and controlled growth. In this study, we found that the longer the thioether chain length, the less isotropic the shape of the particles. Short chain lengths of thioethers (ethyl sulfide and butyl sulfide) produced spherical nanoparticles, whereas longer chain lengths (hexyl sulfide and octyl sulfide) produced cubic nanoparticles. In addition, parameters such as the ligand to precursor ratio also played an important role in the homogeneity of the nanocubes. The Ru NCs were characterized by UV-visible absorbance spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), which supported a face-centered cubic (fcc) structure. Moreover, to demonstrate catalytic efficiency, we studied their ability to reduce benzaldehyde to benzyl alcohol, and the Ru NCs demonstrated an overall 78% efficiency at room temperature.

| S-EPMC9948292 | biostudies-literature

Asymmetric gold-catalyzed lactonizations in water at room temperature.

Project description:Asymmetric gold-catalyzed hydrocarboxylations are reported that show broad substrate scope. The hydrophobic effect associated with in situ-formed aqueous nanomicelles gives good to excellent ee's of product lactones. In-flask product isolation, along with the recycling of the catalyst and the reaction medium, are combined to arrive at an especially environmentally friendly process.

| S-EPMC4193796 | biostudies-literature

Cobalt-Catalyzed Decarboxylative Allylations: Development and Mechanistic Studies.

Project description:In recent years, there has been a concerted drive to develop methods that are greener and more sustainable. Being an earth-abundant transition metal, cobalt offers an attractive substitute for commonly employed precious metal catalysts, though reactions engaging cobalt are still less developed. Herein, we report a method to achieve the decarboxylative allylation of nitrophenyl alkanes, nitroalkanes, and ketones employing cobalt. The reaction allows for the formation of various substituted allylated products in moderate-excellent yields with a broad scope. Additionally, the synthetic potential of the methodology is demonstrated by the transformation of products into versatile heterocyclic motifs. Mechanistic studies revealed an in situ activation of the Co(II)/dppBz precatalyst by the carboxylate salt to generate a Co(I)-species, which is presumed to be the active catalyst.

| S-EPMC10592299 | biostudies-literature

Photo-Induced Ruthenium-Catalyzed Double Remote C(sp<sup>2</sup> )-H / C(sp<sup>3</sup> )-H Functionalizations by Radical Relay.

Project description:Distal C(sp2 )-H and C(sp3 )-H functionalizations have recently emerged as step-economical tools for molecular synthesis. However, while the C(sp2 )-C(sp3 ) construction is of fundamental importance, its formation through double remote C(sp2 )-H/C(sp3 )-H activation has proven elusive. By merging the ruthenium-catalyzed meta-C(sp2 )-H functionalization with an aliphatic hydrogen atom transfer (HAT) process, we, herein, describe the catalyzed twofold remote C(sp2 )-H/C(sp3 )-H functionalizations via photo-induced ruthenium-mediated radical relay. Thus, meta-C(sp2 )-H arene bonds and remote C(sp3 )-H alkane bonds were activated by a single catalyst in a single operation. This process was accomplished at room temperature by visible light-notably without exogenous photocatalysts. Experimental and computational theory studies uncovered a manifold comprising ortho-C-H activation, single-electron-transfer (SET), 1,n-HAT (n=5-7) and σ-activation by means of a single ruthenium(II) catalyst.

| S-EPMC9401009 | 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