Search results for "Suzuki reaction"
showing 10 items of 48 documents
Solid-state cis–trans isomerism in bis(oxamato)palladate(ii) complexes: synthesis, structural studies and catalytic activity
2014
A new generation of bis(oxamato)palladate(II) monomeric complexes has been prepared by using N-2,6-dimethylphenyloxamate (2,6-Me2pma) as the ligand. Four alkaline salts of the complex, namely {[Na(H2O)]2trans-[PdII(2,6-Me2pma)2]}n (1a), {[Na4(H2O)2]cis-[PdII(2,6-Me2pma)2]2}n (1b), {[K4(H2O)3]cis-[PdII(2,6-Me2pma)2]2}n (2), {[Rb4(H2O)3]cis-[PdII(2,6-Me2pma)2]2}n (3) and {[Cs6(H2O)7]trans-[PdII(2,6-Me2pma)2]2cis-[PdII(2,6-Me2pma)2]}n·3nH2O (4), were obtained and structurally characterized by single crystal X-ray diffraction. Both the cis and trans stereoisomers of the [PdII(2,6-Me2pma)2]2− complex anion were isolated in the solid state, in a cation-dependent manner. The trans-isomer as the so…
Synthesis and stereochemical properties of "extended" biphenols bridged by ortho-, meta-, and para-phenylene spacers
2009
A series of isomeric biphenols based on para- (1), meta- (2), and ortho- (3) terphenyl backbones was synthesized. Suzuki cross-coupling methodology was employed for the construction of the terphenyl backbone of their methyl-protected precursors (respectively 8, 13, and 16). Using K2CO3 as the base, the best reaction conditions involved DMF at 100 °C as solvent. Anhydrous conditions greatly improved the yields of the sterically crowded systems (particularly 16). ortho-Terphenyls 3 and 16 exist as mixtures of syn/anti atropisomers in solution. Compound 16 crystallizes in the anti-in form. DFT calculations at the B3LYP/6-311+G(d,p) level indicate that for both compounds the anti-in form is mor…
Evidences of release and catch mechanism in the Heck reaction catalyzed by palladium immobilized on highly cross-linked-supported imidazolium salts
2014
Abstract Palladium (10 wt%) on a highly cross-linked imidazolium-based material was used as catalyst in 0.1 mol% in the Heck reaction between several alkenes and aryl iodides. Products were obtained from good to high yields. Deeper investigations showed a release of Pd species in solution and their capture by the imidazolium-based support. When a sixfold amount of support was employed the re-captured Pd species (0.5–0.6 wt%) were not anymore catalytically active. This result represents a new interesting aspect of this work since the highly cross-linked imidazolium-based material can act also as Pd scavenger avoiding the release of the metal in solution. Important differences between Heck an…
Palladium supported on Halloysite-triazolium salts as catalyst for ligand free Suzuki cross-coupling in water under microwave irradiation
2015
Abstract Environmental friendly halloysite-dicationic triazolium salts (second generation) obtained by subsequent click reactions of a diyne derivative in the presence of 2-azidopropyl-modified halloysite nanotubes, were used as supports for palladium catalyst. Thanks to the high triazolium loading (25%) these materials were able to support higher amount of the metal than that on the monocationic derivative (first generation). Such materials were characterized by thermogravimetric analysis, FT-IR spectroscopy and SEM investigations. The new catalytic system was employed in the ligand free Suzuki cross-coupling under microwave irradiation. A set of solvent, time and% loading of palladium was…
Selective Stepwise Suzuki Cross-Coupling Reaction for the Modelling of Photosynthetic Donor−Acceptor Systems
2009
A Suzuki reaction performed as a selective stepwise substitution of two boryl groups on a diarylporphyrin precursor is reported for straightforward construction of a porphyrin trimer, modeling photosynthetic donor-acceptor systems.
Gold-Catalyzed Suzuki Coupling of ortho -Substituted Hindered Aryl Substrates
2017
International audience; A method that allows hindered ortho-substituted aryl iodides to be efficiently coupled to phenylboronic acid using a gold-catalyzed C-C bond formation is presented. The use of a molecularly-defined dinuclear gold chloride catalytic precursor that is stabilized by a new tetradentate (N,N')-diamino-(P,P')-diphosphino ferrocene hybrid ligand in a Suzuki-type reaction is described for the first time. Electron-rich isopropyl groups on phosphorus were found essen-tial for a superior activity, while the performances of a set of analogous gold dinuclear complexes that were fully characterized by multinuclear NMR spectroscopy and XRD analysis, were investigated. Therefore, ar…
Multi-layered, covalently supported ionic liquid phase (mlc-SILP) as highly cross-linked support for recyclable palladium catalysts for the suzuki re…
2011
The reaction between an excess of 1,4-bis(3-vinylimidazolium-1-yl) bromide and a mercaptopropyl-modified amorphous silica gel or ordered mesoporous silica SBA-15 in the presence of azobisisobutyronitrile (AIBN) afforded new materials, which have a high loading of imidazolium moieties. These materials, which contain a highly cross-linked polymeric network, have been denoted as multi-layered, covalently supported ionic liquid phase (mlc-SILP) and have been used as support for palladium catalysts containing a high loading of the metal (10 wt%). Such materials were characterized by several techniques (13C magic angle spinning nuclear magnetic resonance, the Brunauer–Emmett–Teller technique, sma…
Sustainable carbon–carbon bond formation catalyzed by new oxamate-containing palladium(II) complexes in ionic liquids
2013
Abstract New and versatile bis(oxamato)palladate(II) complexes of formula ( n -Bu 4 N) 2 [Pd(2-Mepma) 2 ]·4H 2 O ( 1a ) and ( n -Bu 4 N) 2 [Pd(4-Mepma) 2 ]·2H 2 O·MeCN ( 1b ) ( n -Bu 4 N + = tetra- n -buthylammonium, 2-Mepma = N -2-methylphenyloxamate and 4-Mepma = N -4-methylphenyloxamate) have been synthesized and characterized by spectroscopic methods and single crystal X-ray diffraction. Each palladium(II) ion in 1a and 1b is four-coordinate with two oxygen and two nitrogen atoms from two fully deprotonated oxamate ligands building a centrosymmetric square planar surrounding. Their catalytic role has been investigated for both Heck and Suzuki coupling reactions using a series of aryl…
Green conditions for the Suzuki reaction using microwave irradiation and a new HNT-supported ionic liquid-like phase (HNT-SILLP) catalyst
2014
A new catalytic system based on modified halloysite nanotubes was employed in the Suzuki reaction under microwave irradiation. A set of solvents, times and bases was screened and the best experimental conditions were obtained when the reactions were carried out for 10 min in water–ethanol at 120 °C in presence of K2CO3 as base. Good recyclability was observed. The new catalytic system was employed using either 1 mol% or 0.1 mol%. The palladium catalyst displayed good activity, allowing the synthesis of several biphenyl compounds in high yield working with only 0.1 mol% palladium loading. The application of microwave irradiation decreased the reaction time and also improved conversion with r…
Bis(oxamato)palladate(II) complexes: synthesis, crystal structure and application to catalytic Suzuki reaction
2015
New bis(oxamato)palladate(II) complexes, [Pd(H2O)4][Pd(2,6-Me2pma)2]·2H2O (1), (n-Bu4N)2[Pd(2,6-Me2pma)2]·2H2O (2a), and (n-Bu4N)2[Pd(2,6-Me2pma)2]·2CHCl3 (2b) (2,6-Me2pma = N-2,6-dimethylphenyoxamate and n-Bu4N+ = tetra-n-butylammonium), have been synthesized and the structures of 1 and 2b characterized by single-crystal X-ray diffraction. Complex 1 is a double salt constituted by tetraaquapalladium(II) cations and bis(oxamato)palladate(II) anions interlinked by hydrogen bonds. The palladium(II) ions in 1 are four-coordinate with two oxygens and two nitrogens from two fully deprotonated oxamate ligands (anion), and four water molecules (cation) building centrosymmetric square-planar surrou…