Browse
Submit Data
Databases
API
Help

Dataset Information

14 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

C(sp³ )-H Arylation Promoted by a Heterogeneous Palladium-N-Heterocyclic Carbene Complex in Batch and Continuous Flow.

ABSTRACT: A heterogeneous reusable palladium(II)-bis(N-heterocyclic carbene) catalyst was prepared and shown to catalyze the intramolecular C(sp³ )-H activation/cyclization of N-alkyl-2-bromoanilines furnishing indolines. This new catalytic system was based on a bis-imidazolium ligand immobilized on a spaced cross-linked polystyrene support. The iodide ligands on the catalyst played a central role in the efficiency of the process occurring through a "release and catch" mechanism. The heterogeneous nature of the catalyst was further exploited in the design of a continuous-flow protocol that allowed a more efficient recovery and reuse of the catalyst, as well as a very fast and safe procedure.

SUBMITTER: Ferlin F

PROVIDER: S-EPMC9303704 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

A Cooperative N-Heterocyclic Carbene/Palladium Catalysis System.

Project description:N-heterocyclic carbenes (NHC) have been extensively studied as organocatalysts and ligands for transition metals, but the successful integration of NHCs and late transition metals in cooperative catalysis remains an underexplored area. We have developed a cooperative palladium-catalyzed allylation of NHC-activated aldehydes to access a variety of 3-allyl dihydrocoumarin derivatives. Kinetic experiments support a cooperative pathway for this transformation.

| S-EPMC4212655 | biostudies-literature

A tandem dearomatization/rearomatization strategy: enantioselective N-heterocyclic carbene-catalyzed α-arylation.

Project description:In this study, the first example of the carbene-catalyzed tandem dearomatization/rearomatization reaction of azonaphthalenes with α-chloroaldehydes is described. This protocol enables the efficient assembly of chiral dihydrocinnolinone derivatives in good yields with excellent enantioselectivities (up to 99% ee). Moreover, this strategy enables not only the highly enantioselective NHC-catalyzed nucleophilic aromatic substitution, but also a formal Csp2-Csp3 bond formation.

| S-EPMC6385844 | biostudies-other

Enhancing stability by trapping palladium inside N-heterocyclic carbene-functionalized hypercrosslinked polymers for heterogeneous C-C bond formations.

Project description:Catalyst deactivation caused by the aggregation of active metal species in the reaction process poses great challenges for practical applications of supported metal catalysts in solid-liquid catalysis. Herein, we develop a hypercrosslinked polymer integrated with N-heterocyclic carbene (NHC) as bifunctional support to stabilize palladium in heterogeneous C-C bond formations. This polymer supported palladium catalyst exhibits excellent stability in the one-pot fluorocarbonylation of indoles to four kinds of valuable indole-derived carbonyl compounds in cascade or sequential manner, as well as the representative Suzuki-Miyaura coupling reaction. Investigations on stabilizing effect disclose that this catalyst displays a molecular fence effect in which the coordination of NHC sites and confinement of polymer skeleton contribute together to stabilize the active palladium species in the reaction process. This work provides new insight into the development of supported metal catalysts with high stability and will also boost their efficient applications in advanced synthesis.

| S-EPMC7994585 | biostudies-literature

Ligand-promoted palladium-catalyzed β-methylene C-H arylation of primary aldehydes.

Project description:The transient directing group (TDG) strategy allowed long awaited access to the direct β-C(sp3)-H functionalization of unmasked aliphatic aldehydes via palladium catalysis. However, the current techniques are restricted to terminal methyl functionalization, limiting their structural scopes and applicability. Herein, we report the development of a direct Pd-catalyzed methylene β-C-H arylation of linear unmasked aldehydes by using 3-amino-3-methylbutanoic acid as a TDG and 2-pyridone as an external ligand. Density functional theory calculations provided insights into the reaction mechanism and shed light on the roles of the external and transient directing ligands in the catalytic transformation.

| S-EPMC9132077 | biostudies-literature

Regioselective allene hydrosilylation catalyzed by N-heterocyclic carbene complexes of nickel and palladium.

Project description:Regioselective methods for allene hydrosilylation have been developed, with regioselectivity being governed primarily by the choice of metal. Alkenylsilanes are produced via nickel catalysis with larger N-heterocyclic carbene (NHC) ligands, and allylsilanes are produced via palladium catalysis with smaller NHC ligands. These complementary methods allow either regioisomeric product to be obtained with exceptional regiocontrol.

| S-EPMC3838997 | biostudies-literature

N-Heterocyclic Carbene Modified Palladium Catalysts for the Direct Synthesis of Hydrogen Peroxide.

Project description:Heterogeneous palladium catalysts modified by N-heterocyclic carbenes (NHCs) are shown to be highly effective toward the direct synthesis of hydrogen peroxide (H2O2), in the absence of the promoters which are typically required to enhance both activity and selectivity. Catalytic evaluation in a batch regime demonstrated that through careful selection of the N-substituent of the NHC it is possible to greatly enhance catalytic performance when compared to the unmodified analogue and reach concentrations of H2O2 rivaling that obtained by state-of-the-art catalysts. The enhanced performance of the modified catalyst, which is retained upon reuse, is attributed to the ability of the NHC to electronically modify Pd speciation.

| S-EPMC9449981 | biostudies-literature

Visible-Light-Mediated Selective Arylation of Cysteine in Batch and Flow.

Project description:A mild visible-light-mediated strategy for cysteine arylation is presented. The method relies on the use of eosin Y as a metal-free photocatalyst and aryldiazonium salts as arylating agents. The reaction can be significantly accelerated in a microflow reactor, whilst allowing the in situ formation of the required diazonium salts. The batch and flow protocol described herein can be applied to obtain a broad series of arylated cysteine derivatives and arylated cysteine-containing dipeptides. Moreover, the method was applied to the chemoselective arylation of a model peptide in biocompatible reaction conditions (room temperature, phosphate-buffered saline (PBS) buffer) within a short reaction time.

| S-EPMC5656832 | biostudies-literature

N-Heterocyclic Carbene Ligand-Enabled C(sp(3))-H Arylation of Piperidine and Tetrahydropyran Derivatives.

Project description:Pd(II)-catalyzed C(sp(3))-H arylation of saturated heterocycles with a wide range of aryl iodides is enabled by an N-heterocyclic carbene (NHC) ligand. A C(sp(3))-H insertion step by the Pd(II)/NHC complex in the absence of ArI is demonstrated experimentally for the first time. Experimental data suggests that the previously established NHC-mediated Pd(0)/Pd(II) catalytic manifold does not operate in this reaction. This transformation provides a new approach for diversifying pharmaceutically relevant piperidine and tetrahydropyran ring systems.

| S-EPMC4805524 | biostudies-literature

Synergy between supported ionic liquid-like phases and immobilized palladium N-heterocyclic carbene-phosphine complexes for the Negishi reaction under flow conditions.

Project description:The combination of supported ionic liquids and immobilized NHC-Pd-RuPhos led to active and more stable systems for the Negishi reaction under continuous flow conditions than those solely based on NHC-Pd-RuPhos. The fine tuning of the NHC-Pd catalyst and the SILLPs is a key factor for the optimization of the release and catch mechanism leading to a catalytic system easily recoverable and reusable for a large number of catalytic cycles enhancing the long-term catalytic performance.

| S-EPMC7418103 | biostudies-literature

Potent Anticancer Activity with High Selectivity of a Chiral Palladium N-Heterocyclic Carbene Complex.

Project description:Five enantiomeric pairs of palladium complexes of 1,2,4-triazole-derived chiral N-heterocyclic carbene ligands were investigated to probe the influence of chirality on the compound's anticancer activity. Although no chirality-related influence was observed for any of the enantiomeric pair, strong anticancer activity was seen for a particular pair, (1S,2S,5R)-1c and (1R,2R,5S)-1c, which was significantly more active than the benchmark drug cisplatin for human breast cancer cells, MCF-7 (ca. 24-27-fold), and human cervical cancer cells, HeLa (ca. three- to fourfold). Broadening its scope of application, (1R,2R,5S)-1c also exhibited antiproliferative activity against lung cancer (A549), skin cancer (B16F10), and multidrug-resistant mammary tumor (EMT6/AR1) cell lines. Interestingly, (1R,2R,5S)-1c displayed 8- and 16-fold stronger antiproliferative activity toward B16F10 and MCF-7 relative to their respective noncancerous counterparts, L929 (fibroblast skin cells) and MCF10A (epithelial breast cells), thereby upholding the potential of these complexes for further development as anticancer agents. (1R,2R,5S)-1c inhibited tumor-cell proliferation by blocking the cells at the G2 phase. (1R,2R,5S)-1c caused DNA damage in MCF-7 cells, leading to mitochondrial reactive oxygen species production and subsequently cell death. We also present evidence indicating that (1R,2R,5S)-1c induced p53-dependent programmed cell death in MCF-7 cells.

| S-EPMC6044915 | biostudies-literature