Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Site-Selective Suzuki-Miyaura and Sonogashira Cross Coupling Reactions of the Bis(triflate) of 2,4'-Bis(hydroxy)diphenyl Sulfone.

ABSTRACT: Described is the synthesis of novel arylated and alkynylated 2,4'-diphenyl sulfones based on what are, to the best of our knowledge, the first palladium(0)-catalyzed cross-coupling reactions of bis(triflates) of 2,4'-bis(hydroxy)diphenyl sulfone. The reactions proceed with very good site-selectivity.

SUBMITTER: Khera RA

PROVIDER: S-EPMC7162099 | biostudies-literature | 2012 Mar

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Site-Selective Suzuki-Miyaura and Sonogashira Cross Coupling Reactions of the Bis(triflate) of 2,4'-Bis(hydroxy)diphenyl Sulfone.

Khera Rasheed Ahmad RA Ali Asad A Hussain Munawar M Ibad Muhammad Farooq MF Villinger Alexander A Langer Peter P

ChemCatChem 20120201 3

Described is the synthesis of novel arylated and alkynylated 2,4'-diphenyl sulfones based on what are, to the best of our knowledge, the first palladium(0)-catalyzed cross-coupling reactions of bis(triflates) of 2,4'-bis(hydroxy)diphenyl sulfone. The reactions proceed with very good site-selectivity. ...[more]

PMID: 32313586

Similar Datasets

Crystal structures of three 4-substituted-2,2'-bipyridines synthesized by Sonogashira and Suzuki-Miyaura cross-coupling reactions.

Project description:Facile synthetic routes for three 4-substituted 2,2'-bi-pyridine derivatives, 4-[2-(4-methyl-phenyl)-ethyn-yl]-2,2'-bi-pyridine, C19H14N2, (I), 4-[2-(pyridin-3-yl)ethyn-yl]-2,2'-bi-pyridine, C17H11N3, (II), and 4-(indol-4-yl)-2,2'-bi-pyridine, C18H13N3, (III), via Sonogashira and Suzuki-Miyaura cross-coupling reactions, respect-ively, are described. As indicated by X-ray analysis, the 2,2'-bi-pyridine core, the ethyl-ene linkage and the substituents of (I) and (II) are almost planar [dihedral angles between the two ring systems: 8.98 (5) and 9.90 (6)° for the two mol-ecules of (I) in the asymmetric unit and 2.66 (14)° for (II)], allowing π-conjugation. On the contrary, in (III), the indole substituent ring is rotated significantly out of the bi-pyridine plane [dihedral angle = 55.82 (3)°], due to steric hindrance. The crystal packings of (I) and (II) are dominated by π-π inter-actions, resulting in layers of mol-ecules parallel to (30-2) in (I) and columns of mol-ecules along the a axis in (II). The packing of (III) exhibits zigzag chains of mol-ecules along the c axis inter-acting through N-H⋯N hydrogen bonds and π-π inter-actions. The contributions of unknown disordered solvent mol-ecules to the diffraction intensities in (II) were removed with the SQUEEZE [Spek (2015 ▸). Acta Cryst. C71, 9-18] algorithm of PLATON. The given chemical formula and other crystal data do not take into account these solvent mol-ecules.

| S-EPMC5382633 | biostudies-literature

Bis(dialkylphosphino)ferrocene-Ligated Nickel(II) Precatalysts for Suzuki-Miyaura Reactions of Aryl Carbonates.

Project description:Aryl carbonates, a common protecting group in synthetic organic chemistry, are potentially valuable electrophiles in cross-coupling reactions. Here, after performing a thorough evaluation of different precatalysts, we demonstrate that (dcypf)Ni(2-ethylphenyl)(Br) (dcypf = 1,1-bis-(dicyclohexylphosphino)ferrocene) is an efficient precatalyst for Suzuki-Miyaura reactions using a variety of aryl carbonates as substrates. Mechanistic studies indicate that (dcypf)Ni(2-ethylphenyl)(Br), which contains a bidentate phosphine that binds in a trans geometry, is an effective precatalyst for these reactions for two reasons: (i) it rapidly forms the Ni(O) active species and (ii) it minimizes comproportionation reactions between the Ni(O) active species and both the unactivated Ni(II) precatalyst and on-cycle Ni(II) complexes to form catalytically inactive Ni(I) species. In contrast, the state of the art precatalyst (dppf)Ni(o-tolyl)(Cl) (dppf = 1,1-bis(diphenylphosphino)ferrocene), which contains a bidentate phosphine that binds in a cis geometry, forms Ni(I) species during activation and is essentially inactive for aryl carbonate couplings. Although the exact reasons on a molecular level why the dcypf system is more active than the dppf system are unclear, our results indicate that in general Ni catalysts supported by the dcypf ligand will give better performance for catalytic reactions involving substrates which undergo relatively slow oxidative addition, such as aryl carbonates.

| S-EPMC7304551 | biostudies-literature

Synthesis, characterization and evaluation of bulky bis(pyrazolyl)palladium complexes in Suzuki-Miyaura cross-coupling reactions.

Project description:Pyrazole-containing compounds have been used in recent times as ligands to stabilize metal complexes used as pre-catalysts in cross-coupling reactions. With various substituents at various positions in the pyrazole ring, the overall electrophilic and steric properties of the metal complexes can be fine-tuned. Herein, we report the synthesis of bulky pyrazole-based ligands by condensation of methyl 4-(bromomethyl)benzoate or benzyl bromide with various substituted pyrazole compounds. These ligands were utilised in the synthesis of bis(pyrazolyl)palladium(ii) complexes. The complexes' catalytic activity in Suzuki-Miyaura cross-coupling reactions was evaluated. Phenyl bearing pre-catalyst 7, at a catalyst loading of 0.33 mol%, successfully converted 98% of bromobenzene and phenylboronic acid to biphenyl in 4 h at 140 °C, while the tertiary butyl bearing pre-catalyst 8 converted up to 81% of the same substrates to biphenyl. An increase in conversion was seen for all pre-catalysts when an electron-withdrawing substituent was present on the aryl halide substrate, and the opposite was observed when the electron-withdrawing group was present on the phenyl boronic acid.

| S-EPMC9079791 | biostudies-literature

Distinguishing between pathways for transmetalation in Suzuki-Miyaura reactions.

Project description:We report a systematic study of the stoichiometric reactions of isolated arylpalladium hydroxo and halide complexes with arylboronic acids and aryltrihydroxyborates to evaluate the relative rates of the two reaction pathways commonly proposed to account for transmetalation in the Suzuki-Miyaura reaction. On the basis of the relative populations of the palladium and organoboron species generated under conditions common for the catalytic process and the observed rate constants for the stoichiometric reactions between the two classes of reaction components, we conclude that the reaction of a palladium hydroxo complex with boronic acid, not the reaction of a palladium halide complex with trihydroxyborate, accounts for transmetalation in catalytic Suzuki-Miyaura reactions conducted with weak base and aqueous solvent mixtures.

| S-EPMC3041853 | biostudies-literature

Aminophosphine Palladium Pincer-Catalyzed Carbonylative Sonogashira and Suzuki-Miyaura Cross-Coupling with High Catalytic Turnovers.

Project description:This work documents the first palladium pincer complex-catalyzed carbonylative Sonogashira (CS) and carbonylative Suzuki-Miyaura (CSM) cross-coupling. Compared to previous protocols, which employ hazardous and toxic solvents, the aminophosphine pincer complex {[C6H3-2,6-(NHP{piperidinyl}2)2]Pd(Cl)} (III) catalyzes both the cross-coupling reactions in propylene carbonate, an eco-friendly and sustainable polar aprotic solvent. Advantageously, employing III allows the CS cross-coupling to be carried out at a palladium loading of 10-4 mol % and the CSM cross-coupling to be carried out at 10-6 mol %, thus resulting in catalytic turnovers of 105 and 107, respectively. Relative comparison of the pincer complex with conventional palladium precursors Pd(OAc)2 and PdCl2(PPh3)2 shows the efficiency and robustness of the pincer complex in effecting higher catalytic activity at low palladium loadings.

| S-EPMC6648871 | biostudies-literature

Extension and functionalization of an encapsulating macrobicyclic ligand using palladium-catalyzed Suzuki-Miyaura and Sonogashira reactions of iron(ii) dihalogenoclathrochelates with inherent halogen substituents.

Project description:A new approach for performing Suzuki-Miyaura and Sonogashira reactions of iron(ii) dihalogenoclathrochelates, optimizing their reaction conditions (such as temperature, solvent and a palladium-containing catalyst) and the nature of other reagents (such as arylboron components) is elaborated. These palladium-catalyzed reactions are very sensitive to the nature of the macrobicyclic substrates. The reactivity of the leaving halogen atoms correlates with their ability to undergo an oxidative addition, decreasing in the order: I > Br > Cl, and iron(ii) diiodoclathrochelate underwent these C-C cross-couplings under their "classical" conditions. Phenylboronic, 4-carboxyphenylboronic and 6-ethoxy-2-naphthylboronic acids, and the diethyl ether of 4-(ethoxycarbonyl)boronic acid were tested as components of Suzuki-Miyaura reactions in DMF and in THF. The highest yields of the target products were obtained in DMF, while the highest activation was observed with sodium and potassium carbonates. The Suzuki-Miyaura reaction of a diiodoclathrochelate with 6-ethoxy-2-naphthylboronic acid gave the mono- and difunctionalized clathrochelates resulting from the tandem hydrodeiodination - C-C cross-coupling and double C-C cross-coupling reactions, respectively. Its Sonogashira reactions with trimethylsilylacetylene and acetylenecarboxylic acid in THF and in DMF were tested. This palladium-catalyzed reaction with a (CH3)3Si-containing active component gave the target products in a high total yield. The complexes obtained were characterized using elemental analysis, MALDI-TOF, UV-Vis, 1H and 13C{1H} NMR spectroscopy, and by single crystal XRD. Despite the non-equivalence of the ribbed α-dioximate fragments of their molecules, the encapsulated iron(ii) ion is situated almost in the centre of its FeN6-coordination polyhedron, the geometry of which is almost intermediate between a trigonal prism and a trigonal antiprism.

| S-EPMC9079834 | biostudies-literature

Bis[4-(2-hydroxy-ethyl-amino)phen-yl] sulfone.

Project description:The title compound, C(16)H(20)N(2)O(4)S, exhibits a V-shape structure with a dihedral angle of 77.5?(11)° formed by the two benzenel rings. The mol-ecular packing is stabilized by intra-molecular and inter-molecular hydrogen bonds as well as ?-? [3.738?(3)?Å] and C-H?? inter-actions.

| S-EPMC2915238 | biostudies-literature

Suzuki-Miyaura cross-coupling reactions of primary alkyltrifluoroborates with aryl chlorides.

Project description:Parallel microscale experimentation was used to develop general conditions for the Suzuki-Miyaura cross-coupling of diversely functionalized primary alkyltrifluoroborates with a variety of aryl chlorides. These conditions were found to be amenable to coupling with aryl bromides, iodides, and triflates as well. The conditions that were previously identified through similar techniques to promote the cross-coupling of secondary alkyltrifluoroborates with aryl chlorides were not optimal for the primary alkyltrifluoroborates, thus demonstrating the value of parallel experimentation to develop novel, substrate specific results.

| S-EPMC2696385 | biostudies-literature

Suzuki-Miyaura cross-coupling reactions of benzyl halides with potassium aryltrifluoroborates.

Project description:[reaction: see text] The palladium-catalyzed cross-coupling of potassium aryltrifluoroborates with benzylic halides occurs in good yield with high functional group tolerance. The increased stability of potassium aryltrifluoroborates compared to other boron coupling partners makes this an effective route to functionalized methylene-linked biaryl systems.

| S-EPMC2515367 | biostudies-literature

Atomically dispersed palladium catalyses Suzuki-Miyaura reactions under phosphine-free conditions.

Project description:Single-atom catalysts have emerged as a new frontier in catalysis science. However, their applications are still limited to small molecule activations in the gas phase, the classic organic transformations catalyzed by single-atom catalysts are still rare. Here, we report the use of a single-atom Pd catalyst for the classic Suzuki-Miyaura carbon-carbon coupling reaction under phosphine-free and open-air conditions at room temperature. The single-atom Pd catalyst is prepared through anchoring Pd on bimetal oxides (Pd-ZnO-ZrO2). The significant synergetic effect of ZnO and ZrO2 is observed. The catalyst exhibits high activity and tolerance of a wide scope of substrates. Characterization demonstrates that Pd single atoms are coordinated with two oxygen atoms in Pd-ZnO-ZrO2 catalyst. The catalyst can be fabricated on a multi-gram scale using a simple in situ co-precipitation method, which endows this catalytic system with great potential in practical applications.

| S-EPMC9814916 | 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