Extended knowledge of 1,1′-Bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex

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Oligo- and polymeric PdII and PtII using pyridyl carboxylate spacers for topology control

An array of PdII and PtII supramolecular assemblies have been constructed using pyridyl carboxylates as spacers and phosphines [(C5H4PPh2)2Fe (dppf) and PPh 3)] as supporting ligands. Different molecular topologies such as squares, triangles, rectangles, and polymers can be controlled by the spatial and directional character of the spacer. A change of the denticity of the phosphine does not affect the topological outcome. Significant differences, however, are observed for the congeneric analogues, with PdII showing a more pronounced tendency toward coordination polymer formation and its attached carboxyl a higher affinity toward Ag+. The ability of these assemblies to capture cations, such as Na+ in [Pt3Na(3- NC5H4CO2)3(OTf)3(PPh 3)6]+ through hydrogen bonding or Ag + in [PdAg(2-NC5H4CO2)(OTf) 2(dppf)] through dative bonding, is described and compared. All of the complexes are structurally characterized by single-crystal X-ray crystallography.

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Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

New explortion of 1,1′-Bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex

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Suzuki-Miyaura Diversification of Amino Acids and Dipeptides in Aqueous Media

The Suzuki-Miyaura derivatisation of free amino acids, peptides and proteins is an attractive area with considerable potential utility for medicinal chemistry and chemical biology. Here we report the modification of unprotected and Boc-protected aromatic amino acids and dipeptides in aqueous media, enabling heteroarylation and vinylation. We systematically investigate the impact of the peptide backbone and adjacent amino acid residues upon the reaction. Our studies reveal that although asparagine and histidine hinder the reaction, by utilising dppf, a ferrocene-based bidentate phosphine ligand, cross coupling of halophenylalanine or halotryptophan adjacent to such a residue could be enabled. Our studies reveal dppf to have good compatibility with all unprotected, proteinogenic amino acid side chains.

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

Some scientific research about 1,1′-Bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex

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Copper-catalyzed amination of (bromophenyl)ethanolamine for a concise synthesis of aniline-containing analogues of NMDA NR2B antagonist ifenprodil

An operationally simple and concise synthesis of anilinoethanolamines, as NMDA NR2B receptor antagonist ifenprodil analogues, was developed via a copper-catalyzed amination of the corresponding bromoarene. Coupling was achieved with linear primary alkylamines, alpha,omega-diamines, hexanolamine and benzophenone imine, as well as with aqueous ammonia, in good yields using CuI and N,N-diethylsalicylamide, 2,4-pentadione or 2-acetylcyclohexanone as catalytic systems. Amination with ethylene diamine was efficient even in the absence of an additive ligand, whereas no reaction occurred with ethanolamine whatever the conditions used. The anilinoethanolamines were evaluated as NR2B receptor antagonists in a functional inhibition assay. Aminoethylanilines displayed inhibition effects close to that of ifenprodil. The Royal Society of Chemistry.

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Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Highly regio- and stereoselective synthesis of multialkylated olefins through carbozirconation of alkynylboronates and sequential Negishi and Suzuki-Miyaura coupling reactions

Two Nobel couplings: The synthesis of tri- and tetraalkylated olefins has been achieved (see scheme). These multialkylated olefins were prepared by the zirconocene-mediated carbometalation of 1-alkynylboronates and subsequent sequential C-C bond formation with Negishi and Suzuki-Miyaura cross-coupling reactions using beta-hydrogen-containing alkylzinc reagents and alkyl electrophiles as coupling partners. Copyright

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

Brief introduction of 1,1′-Bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex

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Synthesis, characterization and molecular recognition of a bis-platinum terpyridine dimer

A novel bis-platinum(ii) terpyridine-based macrocycle has been quantitatively obtained by self-assembly; the Pt(ii) host binds neutral planar and electron-rich aromatic guests with good selectivity in DMSO. The Royal Society of Chemistry.

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Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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A 3-aryl-2-cyclopenten-1-one compound method for the synthesis of (by machine translation)

The invention relates to a kind of the following formula (III) shown in the 3 […] aryl -2 the […] cyclopentene -1 the method for synthesizing compound of […], the method comprising: under a nitrogen atmosphere, in an organic solvent, the catalyst, in the presence of alkali and, the following formula (I) compounds and the following formula (II) compound in 40 the […] 50 C reaction under the 1 […] 2 hours, then raise the temperature, in the 70 […] 80 C reaction under the 4 […] 6 hours, so as to obtain the compound of said formula (III), wherein R 1 to C 1 ? C 6 alkyl or C 1 ? C 6 alkoxythiophene; R 2 to C 1 ? C 6 alkyl or halogenated C 1 ? C 6 alkyl; X is or S N; n is 1 or 2. The stated method, through catalyst, alkali, organic solvent, etc. of the auxiliary agent and combined and synergies, and through the control of reaction temperature, thus the objective product may be obtained in a high yield, in the field of organic synthesis technology has good prospects and research potential application of. (by machine translation)

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Substituted Metal Carbonyls. Part 21. as a Metalloligand in Heteropolymetallic Aggregates of AuI, PdII and PtII. Crystal and Molecular Structures of 2> and

The complexes behave like a monodentate phosphine ligand and displace the labile ligands from , trans- and cis- (dmso = dimethyl sulfoxide) to yield the corresponding dppf-bridged heteropolymetallic complexes of general formula y> (M’ = Au, x = y = 1; M’ = Pd or Pt, x = y = 2).Only the trans isomers have been isolated for PdII and PtII.Isomerisation of the M’ = Pt, M = Cr complex to the cis form, followed by partial elimination of to form , after 3d in CDCl3 was revealed by NMR spectroscopy.The solution characteristics of both geometrical isomers of the representative M’ = Pt, M = Cr complex have been established by two-dimensional NMR studies.UV-Photolytic degradation of the M’ = Pd or Pt, M complexes generally gave , , and .The molecular structures of trans-2> and have been determined.The former represents a trimetallic pentanuclear aggregate and the latter a metalloligand with a pendant phosphine on a bimetallic complex.Cyclic voltammetry of all the complexes has been examined and generally reveals one chemically reversible phosphinoferrocene-based oxidation, followed by an irreversible oxidation of the complex.

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Syntheses with organoboranes. XIII. Synthesis of omega-(4-bromophenyl)alkanoic acids and their borylation

omega-(4-Bromophenyl)alkanoic acids 2c-e were obtained from 1-bromo-4-alkenylbenzenes 5c-e by hydroboration-thermal isomerization-oxidation. Their esters 11c-e were transformed in good yields into the corresponding boronates 12c-e by the cross-coupling reaction with (10) in an ionic liquid, [bmim][BF4]. The use of pinacolborane for the coupling reaction in the ionic liquid gave debromination products, and low yields of 12c-e. Ethyl 3-(4-bromophenyl)propanoate (7c) was transformed into ethyl 3-(4-[1,3,2]dioxaborolanyl)propanoate (9c) by the cross-coupling with [2,2?]bi[[1,3,2]dioxaborinanyl].

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

Brief introduction of

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Wide bite angle diphosphine ligands were used to prepare [(diphosphine)M(2-(diphenylphosphino)pyridine)]2+ complexes (M = Pd, Pt). Except for the ligand with the largest bite angle, 2-(diphenylphosphino) pyridine coordinates in a bidentate mode leading to bis-chelate complexes. In the case of Xantphos (9,9-dimethyl-4,5-bis(diphenylphosphino)-xanthene, betan = 111) two types of complexes are formed, in which 2-(diphenylphosphino)pyridine coordinates in a mono- or bidentate fashion, respectively. The crystal structures of three of the Pt complexes were determined. The X-ray crystal structure of [(Xantphos)-Pt(2-(diphenylphosphino) pyridine)]2+ shows that Xantphos coordinates in a tridentate P,O,P fashion. Under dihydrogen pressure, the pyridyl moiety in the platinum complexes can de-coordinate to provide a vacant coordination site at the metal center. Furthermore it can act as an internal base to assist the heterolytic cleavage of dihydrogen. The reaction yields a platinum hydride with a protonated pyridine moiety in close proximity to one another. The structure as well as the reactivity of the complexes towards dihydrogen is governed by the steric requirements of the diphosphines. The crystal structure of [(dppf)PtH(2- (diphenylphosphino)pyridinium)](OTf)2 has been determined. Palladium complexes containing DPEphos or Xantphos decompose under dihydrogen pressure. In the case of dppf slow heterolytic splitting of dihydrogen occurs to form the hydride complex [(dppf)PdH(2-(diphenylphosphino)pyridinium)](OTf)2 which contains a protonated 2-(diphenylphosphino)pyridine ligand. In solution, this compound slowly undergoes P-C bond cleavage of the 2-(diphenylphosphino) pyridine ligand to form [(dppf)Pd(PHPh2)(eta1-C 5H4NH)](OTf)2. When the 6-methyl-2- pyridyldiphenylphosphine ligand is used, the reaction of the palladium complex with dihydrogen is very fast and the hydride complex immediately rearranges to the diphenylphosphino compound resulting from P-C bond cleavage.

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

Some scientific research about

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A procedure was developed for the synthesis of 4,6-diamino- and 4,6- or 6,4-arylaminoquinolines by palladium-catalyzed C-N- and/or C-C-cross-coupling of 6-bromo-4-chloroquinoline.

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method