Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Meta-Selective C-H Arylation of Aromatic Alcohols with a Readily Attachable and Cleavable Molecular Scaffold.

ABSTRACT: The first example of meta-selective C-H arylations of arene alcohol-based substrates is described. The strategy involves the combination of the transient norbornene strategy with the quinoline-based acetal scaffold to achieve the formation of biaryl compounds. Both a two-step meta-arylation/scaffold cleavage process and a total telescoping procedure are described, highlighting the convenient attributes of attachment, removal, and recovery of the acetal scaffold. Moreover, the meta-arylated compounds can be further derivatized via ortho-selective functionalizations. These processes establish a foundation for catalytic polyfunctionalization of alcohol-based compounds.

SUBMITTER: Li Q

PROVIDER: S-EPMC5984653 | biostudies-literature | 2017 Aug

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Meta-Selective C-H Arylation of Aromatic Alcohols with a Readily Attachable and Cleavable Molecular Scaffold.

Li Qiankun Q Ferreira Eric M EM Ferreira Eric M EM

Chemistry (Weinheim an der Bergstrasse, Germany) 20170807 48

The first example of meta-selective C-H arylations of arene alcohol-based substrates is described. The strategy involves the combination of the transient norbornene strategy with the quinoline-based acetal scaffold to achieve the formation of biaryl compounds. Both a two-step meta-arylation/scaffold cleavage process and a total telescoping procedure are described, highlighting the convenient attributes of attachment, removal, and recovery of the acetal scaffold. Moreover, the meta-arylated compo ...[more]

PMID: 28675786

Similar Datasets

Palladium(II)-Catalyzed ortho-Arylation of Aromatic Alcohols with a Readily Attachable and Cleavable Molecular Scaffold.

Project description:A palladium(II)-catalyzed C-H arylation process of alcohols has been developed. The strategy utilizes a novel quinoline-based hemiacetal scaffold that can direct the selective C-H bond functionalization. This reaction provides a useful method to construct biaryl compounds of benzyl alcohols in good to excellent yields. The new molecular scaffold can be readily attached, removed, and recovered.

| S-EPMC5984652 | biostudies-literature

The design of a readily attachable and cleavable molecular scaffold for ortho-selective C-H alkenylation of arene alcohols.

Project description:We describe herein the design of a novel molecular scaffold that can induce facile oxidative olefinations when attached to alcohols. Benzylic, homo-, and bishomobenzylic alcohols are utilized. The scaffold can act as a protecting group for the alcohol in other transformations, and it is recoverable in excellent yield. The overall sequence can also be telescoped without purifications of intermediates, representing a net alcohol-based directed ortho-alkenylation.

| S-EPMC5966905 | biostudies-literature

Metallaphotoredox-enabled deoxygenative arylation of alcohols.

Project description:Metal-catalysed cross-couplings are a mainstay of organic synthesis and are widely used for the formation of C-C bonds, particularly in the production of unsaturated scaffolds1. However, alkyl cross-couplings using native sp3-hybridized functional groups such as alcohols remain relatively underdeveloped2. In particular, a robust and general method for the direct deoxygenative coupling of alcohols would have major implications for the field of organic synthesis. A general method for the direct deoxygenative cross-coupling of free alcohols must overcome several challenges, most notably the in situ cleavage of strong C-O bonds3, but would allow access to the vast collection of commercially available, structurally diverse alcohols as coupling partners4. We report herein a metallaphotoredox-based cross-coupling platform in which free alcohols are activated in situ by N-heterocyclic carbene salts for carbon-carbon bond formation with aryl halide coupling partners. This method is mild, robust, selective and most importantly, capable of accommodating a wide range of primary, secondary and tertiary alcohols as well as pharmaceutically relevant aryl and heteroaryl bromides and chlorides. The power of the transformation has been demonstrated in a number of complex settings, including the late-stage functionalization of Taxol and a modular synthesis of Januvia, an antidiabetic medication. This technology represents a general strategy for the merger of in situ alcohol activation with transition metal catalysis.

| S-EPMC8643278 | biostudies-literature

Cleavable and tunable cysteine-specific arylation modification with aryl thioethers.

Project description:Cysteine represents an attractive target for peptide/protein modification due to the intrinsic high nucleophilicity of the thiol group and low natural abundance. Herein, a cleavable and tunable covalent modification approach for cysteine containing peptides/proteins with our newly designed aryl thioethers via a S N Ar approach was developed. Highly efficient and selective bioconjugation reactions can be carried out under mild and biocompatible conditions. A series of aryl groups bearing different bioconjugation handles, affinity or fluorescent tags are well tolerated. By adjusting the skeleton and steric hindrance of aryl thioethers slightly, the modified products showed a tunable profile for the regeneration of the native peptides.

| S-EPMC8179606 | biostudies-literature

Room temperature, metal-free arylation of aliphatic alcohols.

Project description:Diaryliodonium salts are demonstrated as efficient arylating agents of aliphatic alcohols under metal-free conditions. The reaction proceeds at room temperature within 90 min to give alkyl aryl ethers in good to excellent yields. Aryl groups with electron-withdrawing substituents are transferred most efficiently, and unsymmetric iodonium salts give chemoselective arylations. The methodology has been applied to the formal synthesis of butoxycaine.

| S-EPMC4000167 | biostudies-literature

Selective Oxidation of Biomass-Derived Alcohols and Aromatic and Aliphatic Alcohols to Aldehydes with O2/Air Using a RuO2-Supported Mn3O4 Catalyst.

Project description:Selective catalytic oxidation of carbohydrate-derived 5-hydroxymethylfurfural, furfuryl alcohol, and various aromatic and aliphatic compounds to the corresponding aldehyde is a challenging task. The development of a sustainable heterogeneous catalyst is crucial in achieving high selectivity for the desired aldehyde, especially using O2 or air. In this study, a RuO2-supported Mn3O4 catalyst is reported for the selective oxidation reaction. Treatment of MnO2 molecular sieves with RuCl3 in aqueous formaldehyde solution gives a new type of RuO2-supported Mn3O4 catalyst. Detailed catalyst characterization using powder X-ray diffraction, N2 adsorption, scanning and transmission electron microscopes, diffuse reflectance UV-visible spectrometer, and X-ray photoelectron spectroscopy proves that the RuO2 species are dispersed on the highly crystalline Mn3O4 surface. This catalytic conversion process involves molecular oxygen or air (flow, 10 mL/min) as an oxidant. No external oxidizing reagent, additive, or cocatalyst is required to carry out this transformation. This oxidation protocol affords 2,5-diformylfuran, 2-formylfuran, and other aromatic and aliphatic aldehydes in good to excellent yield (70-99%). Moreover, the catalyst is easily recycled and reused without any loss in the catalytic activity.

| S-EPMC6644874 | biostudies-literature

Selective Hydrogen Atom Abstraction through Induced Bond Polarization: Direct α-Arylation of Alcohols through Photoredox, HAT, and Nickel Catalysis.

Project description:The combination of nickel metallaphotoredox catalysis, hydrogen atom transfer catalysis, and a Lewis acid activation mode, has led to the development of an arylation method for the selective functionalization of alcohol α-hydroxy C-H bonds. This approach employs zinc-mediated alcohol deprotonation to activate α-hydroxy C-H bonds while simultaneously suppressing C-O bond formation by inhibiting the formation of nickel alkoxide species. The use of Zn-based Lewis acids also deactivates other hydridic bonds such as α-amino and α-oxy C-H bonds. This approach facilitates rapid access to benzylic alcohols, an important motif in drug discovery. A 3-step synthesis of the drug Prozac exemplifies the utility of this new method.

| S-EPMC6448405 | biostudies-literature

Iron-Catalyzed Acceptorless Dehydrogenative Coupling of Alcohols With Aromatic Diamines: Selective Synthesis of 1,2-Disubstituted Benzimidazoles.

Project description:Benzimidazoles are important N-heteroaromatic compounds with various biological activities and pharmacological applications. Herein, we present the first iron-catalyzed selective synthesis of 1,2-disubstituted benzimidazoles via acceptorless dehydrogenative coupling of primary alcohols with aromatic diamines. The tricarbonyl (?4-cyclopentadienone) iron complex catalyzed dehydrogenative cyclization, releasing water and hydrogen gas as by-products. The earth abundance and low toxicity of iron metal enable the provision of an eco-friendly and efficient catalytic method for the synthesis of benzimidazoles.

| S-EPMC7317090 | biostudies-literature

Attachable Hydrogel Containing Indocyanine Green for Selective Photothermal Therapy against Melanoma.

Project description:Melanoma is the most lethal form of skin cancer because it spreads easily to other tissues, thereby decreasing the efficiency of its treatment via chemo-, radio-, and surgical therapies. We suggest the application of an attachable hydrogel for the treatment of melanoma whereby the size and amount of incorporated indocyanine green (ICG) for photothermal therapy (PTT) can be controlled. An attachable hydrogel (poly(acrylamide-co-diallyldimethylammonium chloride); PAD) that incorporates ICG as a near-infrared (NIR) absorber was fabricated using a biocompatible polymer. The temperature of PAD-ICG increases under 808 nm laser irradiation. The hydrogel protects the ICG against decomposition; consequently, PAD-ICG can be reused for PTT. The attachment of PAD-ICG to an area with melanoma in mice, with irradiation using a NIR laser, successfully eliminated melanoma. Thus, the data suggest that PAD-ICG is a smart material that could be used for selective target therapy against melanoma in humans.

| S-EPMC7465476 | biostudies-literature

Tuning Molecular Vibrational Energy Flow within an Aromatic Scaffold via Anharmonic Coupling.

Project description:From guiding chemical reactivity in synthesis or protein folding to the design of energy diodes, intramolecular vibrational energy redistribution harnesses the power to influence the underlying fundamental principles of chemistry. To evaluate the ability to steer these processes, the mechanism and time scales of intramolecular vibrational energy redistribution through aromatic molecular scaffolds have been assessed by utilizing two-dimensional infrared (2D IR) spectroscopy. 2D IR cross peaks reveal energy relaxation through an aromatic scaffold from the azido- to the cyano-vibrational reporters in para-azidobenzonitrile (PAB) and para-(azidomethyl)benzonitrile (PAMB) prior to energy relaxation into the solvent. The rates of energy transfer are modulated by Fermi resonances, which are apparent by the coupling cross peaks identified within the 2D IR spectrum. Theoretical vibrational mode analysis allowed the determination of the origins of the energy flow, the transfer pathway, and a direct comparison of the associated transfer rates, which were in good agreement with the experimental results. Large variations in energy-transfer rates, approximately 1.9 ps for PAB and 23 ps for PAMB, illustrate the importance of strong anharmonic coupling, i.e., Fermi resonance, on the transfer pathways. In particular, vibrational energy rectification is altered by Fermi resonances of the cyano- and azido-modes allowing control of the propensity for energy flow.

| S-EPMC7045801 | 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