Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Selectivity, Compatibility, Downstream Functionalization, and Silver Effect in the Gold and Palladium Dual-Catalytic Synthesis of Lactones.

ABSTRACT: The chemo- and regioselectivity and functional group compatibility in gold and palladium cooperatively catalyzed cross-coupling reactions were determined in the synthesis of lactones; the selectivity in the gold and palladium dual-metal catalysis system was distinct from that available for the same class of substrates in systems with only gold catalysis or only palladium catalysis rather than dual catalysis. The dual-catalytic rearrangement reaction selectively promoted oxidative addition at the C-O bond over the C-Br bond, providing a useful C-Br bond handle for downstream functionalization showcased via Suzuki-Miyaura and Sonogashira coupling reactions. Product classes were expanded from isocoumarins to three previously unpublished ring classes: pyrone, indolepyrone, and furopyrone.

SUBMITTER: Al-Amin M

PROVIDER: S-EPMC4195511 | biostudies-literature | 2014 Oct

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Selectivity, Compatibility, Downstream Functionalization, and Silver Effect in the Gold and Palladium Dual-Catalytic Synthesis of Lactones.

Al-Amin Mohammad M Johnson Joel S JS Blum Suzanne A SA

Organometallics 20140909 19

The chemo- and regioselectivity and functional group compatibility in gold and palladium cooperatively catalyzed cross-coupling reactions were determined in the synthesis of lactones; the selectivity in the gold and palladium dual-metal catalysis system was distinct from that available for the same class of substrates in systems with only gold catalysis or only palladium catalysis rather than dual catalysis. The dual-catalytic rearrangement reaction selectively promoted oxidative addition at the ...[more]

PMID: 25328271

Similar Datasets

Mechanistic Studies of Gold and Palladium Cooperative Dual-Catalytic Cross-Coupling Systems.

Project description:Double-label crossover, modified-substrate, and catalyst comparison experiments in the gold and palladium dual-catalytic rearrangement/cross-coupling of allenoates were performed in order to probe the mechanism of this reaction. The results are consistent with a cooperative catalysis mechanism whereby 1) gold activates the substrate prior to oxidative addition by palladium, 2) gold acts as a carbophilic rather than oxophilic Lewis acid, 3) competing olefin isomerization is avoided, 4) gold participates beyond the first turnover and therefore does not serve simply to generate the active palladium catalyst, and 5) single-electron transfer is not involved. These experiments further demonstrate that the cooperativity of both gold and palladium in the reaction is essential because significantly lower to zero conversion is achieved with either metal alone in comparison studies that examined multiple potential gold, palladium, and silver catalysts and precatalysts. Notably, employment of the optimized cocatalysts, PPh3AuOTf and Pd2dba3, separately (i.e., only Au or only Pd) results in zero conversion to product at all monitored time points compared to quantitative conversion to product when both are present in cocatalytic reactions.

| S-EPMC3991925 | biostudies-literature

Gold, Silver, and Palladium Nanoparticles: A Chemical Tool for Biomedical Applications.

Project description:Herein, the role of metal-based nanoparticles (NPs) in biomedical analysis and the treatment of critical deceases been highlighted. In the world of nanotechnology, noble elements such as the gold/silver/palladium (Au/Ag/Pd) NPs are the most promising emerging trend to design bioengineering materials that could to be employed as modern diagnostic tools and devices to combat serious diseases. NPs are considered a powerful and advanced chemical tool to diagnose and to cure critical ailments such as HIV, cancer, and other types of infectious illnesses. The treatment of cancer is the most significant application of nanotechnology which is based on premature tumor detection and analysis of cancer cells through Nano-devices. The fascinating characteristic properties of NPs-such as high surface area, high surface Plasmon resonance, multi-functionalization, highly stable nature, and easy processing-make them more prolific for nanotechnology. In this review article, the multifunctional roles of Au/Ag/Pd NPs in the field of medical science, the physicochemical toxicity dependent properties, and the interaction mechanism is highlighted. Due to the cytotoxicity of Ag/Au/Pd NPs, the conclusion and future remarks emphasize the need for further research to minimize the toxicity of NPs in the bio-medicinal field.

| S-EPMC7283583 | biostudies-literature

Facile synthesis of gold nanocages with silver nanocubes templates dual metal effects enabled SERS imaging and catalytic reduction.

Project description:Silver (Ag) nanomaterials featuring a cubic shape particularly represent supreme class of advance nanomaterials. This work explored a new precursor and its effect on morphological features of silver (Ag) nanocubes (NCs) serving as sacrificial templates for facile synthesis of gold NCs. The AgNCs were initially prepared utilizing sodium thiosulphate (Na2S2O3) as relatively stable S2- producing species along with a soft etchant source KCl. The effects of different potassium halides were evaluated to grasp control over seed mediated growth of Ag nanocubes. Taking the advantages of dual metallic properties, Ag@4MBA@AuNCs nanostructure was synthesized using 4-mercaptobenzoic acid (4MBA) as a Raman reporter molecule. This nanostructure showed 1010-times enhancement in surface enhanced Raman scattering (SERS) signal, leading to a highly sensitive imaging probe for the detection of even three breast cancer cells (MCF-7 cells) in vitro. Subsequently, the oxidative nanopeeling well accompanied by incorporation of Au/Ag alloy nanoparticles on AuNCs corona assembly was achieved, which facilitated the catalytic reduction of toxic nitrophenol to eco-friendly aminophenol. Such sophisticated and engineered nanoassemblies possess broad applications in bioanalysis.

| S-EPMC10603383 | biostudies-literature

Accessing Elaborated 2,1-Borazaronaphthalene Cores Using Photoredox/Nickel Dual-Catalytic Functionalization.

Project description:A highly effective method for derivatizing 2,1-borazaronaphthalene cores using ammonium alkylbis(catecholato)silicates via photoredox/nickel dual catalysis is reported. By forging C(sp)(3)-C(sp)(2) bonds via this approach, alkyl fragments with various functional groups can be introduced to the azaborine core, affording previously inaccessible heterocyclic isosteres in good to excellent yields. The base-free, room-temperature conditions outlined allow sensitive functional group tolerance, even permitting the cross-coupling of unprotected primary and secondary amines.

| S-EPMC5373477 | biostudies-literature

Synthesis and Catalytic Activity of Pluronic Stabilized Silver-Gold Bimetallic Nanoparticles.

Project description:In this report, we demonstrate a rapid, simple, and green method for synthesizing silver-gold (Ag-Au) bimetallic nanoparticles (BNPs). We used a novel modification to the galvanic replacement reaction by suspending maltose coated silver nanoparticles (NPs) in ? 2% aqueous solution of EO100PO65EO100 (Pluronic F127) prior to HAuCl4 addition. The Pluronic F127 stabilizes the BNPs, imparts biocompatibility, and mitigates the toxicity issues associated with other surfactant stabilizers. BNPs with higher Au:Ag ratios and, subsequently, different morphologies were successfully synthesized by increasing the concentration of gold salt added to the Ag NP seeds. These BNPs have enhanced catalytic activities than typically reported for monometallic Au or Ag NPs (? 2-10 fold) of comparable sizes in the sodium borohydride reduction of 4-nitrophenol. The 4-nitrophenol reduction rates were highest for partially hollow BNP morphologies.

| S-EPMC4286189 | biostudies-literature

Elucidating the reaction mechanism of a palladium-palladium dual catalytic process through kinetic studies of proposed elementary steps.

Project description:In the synergistic dual catalytic process, the kinetics of the catalytic cycles must be balanced for the successful outcome of the reaction. Therefore, the analysis of the kinetics of the independent catalytic cycles is essential for such reactions, as it enables their relational optimization as well as their design. Here we describe an analysis of the mechanism of a catalytic synergistic bimetallic reaction through the experimental study of a palladium-catalysed cross-coupling of aryl halides with terminal alkynes, an example of a monometallic dual catalytic process. The proposed mechanism of the investigated reaction was disassembled into two palladium catalytic cycles and further into elementary reactions, and each step was studied independently. The described mechanistic analysis allowed us to identify the rate-determining step of the catalytic process by comparing the rates of the elementary reactions under similar reaction conditions, balanced kinetics of the palladium catalytic cycles, and also in which step which reagent enters the catalytic cycle and how.

| S-EPMC10024772 | biostudies-literature

Isolated Effects of Surface Ligand Density on the Catalytic Activity and Selectivity of Palladium Nanoparticles.

Project description:Alkanethiolate-capped palladium nanoparticles (PdNPs) have previously been synthesized by using a modified Brust-Schiffrin synthesis (using alkanethiosulfate instead of alkanethiol), in which the nanoparticle core size is established during alkanethiosulfate ligand passivation of the nanoparticle nucleation-growth initiated by borohydride reduction. Because of the dependence of core size on the amount of ligand present, surface ligand density decreases with increasing core size. Herein we present a method in which the core size is established independent of ligand addition, allowing the formation of PdNPs with similar core sizes yet different surface ligand densities. In this method, the core size is established during the temporary passivation of growing nanoparticles by borohydride and tetra-N-octylammonium bromide (TOAB), allowing nucleation to reach completion. Various molar equivalents of alkyl thiosulfate are then added, prompting the replacement of borohydride and TOAB and the formation of alkanethiolate-capped PdNPs. The resulting PdNPs were characterized by using 1H NMR, transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and inductively coupled plasma atomic emission spectroscopy (ICP-AES). The overall enhanced catalytic activity of hydrogenation/isomerization of alkenes and dienes was observed for PdNPs with a lower ligand density, proving the isolated effect of surface ligand density from other variations such as core size and shape. Surface ligand density is also shown to influence the hydrogenation/isomerization product selectivity of the catalytic reactions by regulating the formation of certain Pd-substrate intermediates and the kinetic diffusion of surface hydrogen/substrates.

| S-EPMC8171273 | biostudies-literature

Boosting activity and selectivity of glycerol oxidation over platinum-palladium-silver electrocatalysts <i>via</i> surface engineering.

Project description:A series of platinum-palladium-silver nanoparticles with tunable structures were synthesized for glycerol electro-oxidation in both alkaline and acidic solutions. Electrochemical results indicate that the catalysts show superior activity in alkaline solutions relative to acidic solutions. In alkaline solutions, the peak current densities of ammonia-etched samples are approximately twice those of saturated-NaCl-etched samples. Ammonia-etched platinum-palladium-silver (PtPd@Ag-NH3) exhibits a peak current density of 9.16 mA cm-2, which is 18.7 and 10 times those of the Pt/C and Pd/C, respectively. The product distribution was analyzed by high performance liquid chromatography. Seven products including oxalic acid, tartronic acid, glyoxylic acid, glyceric acid (GLA), glyceraldehyde (GALD), glycolic acid, and dihydroxyacetone (DHA) were detected. The NH3·H2O etched samples tend to generate more GALD, while the NaCl etched samples have a great potential to produce DHA. The addition of Pd atoms can facilitate glycerol oxidation pathway towards the direction of GALD generation. The Pt@Ag-NaCl possesses the largest DHA selectivity of 79.09% at 1.3 V, while the Pt@Ag-NH3 exhibits the largest GLA selectivity of 45.01% at 0.5 V. The PtPd@Ag-NH3 exhibits the largest C3/C2 ratio of 17.45. The selectivity and product distribution of glycerol electro-oxidation can be tuned by engineering the surface atoms of the as-synthesized catalysts.

| S-EPMC9419557 | biostudies-literature

Silver and Gold Complexes with NHC-Ligands Derived from Caffeine: Catalytic and Pharmacological Activity.

Project description:N-heterocyclic carbene (NHC) silver(I) and gold(I) complexes have found different applications in various research fields, as in medicinal chemistry for their antiproliferative, anticancer, and antibacterial activity, and in chemistry as innovative and effective catalysts. The possibility of modulating the physicochemical properties, by acting on their ligands and substituents, makes them versatile tools for the development of novel metal-based compounds, mostly as anticancer compounds. As it is known, chemotherapy is commonly adopted for the clinical treatment of different cancers, even though its efficacy is hampered by several factors. Thus, the development of more effective and less toxic drugs is still an urgent need. Herein, we reported the synthesis and characterization of new silver(I) and gold(I) complexes stabilized by caffeine-derived NHC ligands, together with their biological and catalytic activities. Our data highlight the interesting properties of this series as effective catalysts in A3-coupling and hydroamination reactions and as promising anticancer, anti-inflammatory, and antioxidant agents. The ability of these complexes in regulating different pathological aspects, and often co-promoting causes, of cancer makes them ideal leads to be further structurally functionalized and investigated.

| S-EPMC10931745 | biostudies-literature

A bio-inspired synthesis of oxindoles by catalytic aerobic dual C-H functionalization of phenols.

Project description:Nitrogen-containing heterocycles are fundamentally important to the function of pharmaceuticals, agrochemicals and materials. Herein, we report a bio-inspired approach to the synthesis of oxindoles, which couples the energetic requirements of dehydrogenative C-N bond formation to the reduction of molecular oxygen (O2). Our method is inspired by the biosynthesis of melanin pigments (melanogenesis), but diverges from the biosynthetic polymerization. Mechanistic analysis reveals the involvement of CuII-semiquinone radical intermediates, which enable dehydrogenative carbon-heteroatom bond formation that avoids a catechol/quinone redox couple. This mitagates the deleterious polarity reversal that results from phenolic dearomatization, and enables a high-yielding phenolic C-H functionalization under catalytic aerobic conditions. Our work highlights the broad synthetic utility and efficiency of forming C-N bonds via a catalytic aerobic dearomatization of phenols, which is currently an underdeveloped transformation.

| S-EPMC5952266 | 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