Brief introduction of [1,1′-Bis(diphenylphosphino)ferrocene]dichloropalladium(II)

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Selective iodination of the cyclopentadienylruthenium tricarbadecaboranyl complexes 1-(eta5-C5H5)-2-Ph-closo-1,2,3,4- RuC3B7H9 (1) and 1-(eta5-C 5(CH3)5)-2-Ph-closo-1,2,3,4-RuC 3B7H8 (2) to form their mono-iodo derivatives, 1-(eta5-C5H5)-2-Ph-6-I-closo-1,2,3,4-RuC 3B7H9 (3) and 1-(eta5-C 5(CH3)5)-2-Ph-6-I-closo-1,2,3,4-RuC 3B7H8 (4), was achieved in 90% yields by their reactions with ICl in CH2Cl2 solutions. Also isolated in trace amounts from the reaction with 2 was the di-iodo 1-(eta5- C5(CH3)5)-2-Ph-6,11-I2-closo-1,2,3, 4-RuC3B7H7, (5) complex. The sonication-promoted Sonogashira coupling reaction of 3 with terminal acetylenes catalyzed by Pd(dppf)Cl2/CuI yielded the functionalized ruthenatricarbadecaboranyl complexes 1-(eta5-C5H 5)-2-Ph-6-(Ph-C?C)-closo-1,2,3,4-RuC3B 7H8 (6), 1-(eta5-C5H 5)-2-Ph-6-[CH3CH2C(O)OCH2-C?C] -closo-1,2,3,4-RuC3B7H8 (7), 1-(eta5-C5H5)-2-Ph-6-[(eta5- C5H5)Fe(eta5-C5H 4)-C?C]-closo-1,2,3,4-RuC3B7H 8 (8) and 1-(eta5-C5H5)-2-Ph-6- [(CH3)3Si-C?C]-closo-1,2,3,4-RuC3B 7H8 (9). These reactions thus provide a versatile, systematic pathway for the syntheses of a wide variety of new types of functionalized ruthenatricarbadecaboranyl complexes.

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

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Enantiomerically pure L-BPA (4-borono-L-phenylalanine) was synthesized from L-tyrosine or 4-iodo-L-phenylalanine derivatives using the palladium- catalyzed cross-coupling reaction of pinacolborane (2,3-dimethyl-2,3- butanediolatoboron). Cbz-Tyr(Nf)-OBzl (2b) underwent the cross-coupling reaction with pinacolborane (1) in the presence of [PdCl2(PPh3)2] catalyst to give N-benzyloxycarbonyl-4-(2,3-dimethyl-2,3-butanediolatoboryl)-L- phenylalanine benzyl ester (3a) in 58% yield. The reaction of the 4-iodo-L- phenylalanine derivatives, such as N-benzyloxycarbonyl-4-iodo-L-phenylalanine benzyl ester (2c), N,N-dibenzyl-4-iodo-L-phenylalanine benzyl ester (2d), (4S)-3-benzyloxycarbonyl-4-(4-iodobenzyl)-5-oxazolidinone (2e), and (4S)-3-t- butyloxycarbonyl-4-(4-iodobenzyl)-5-oxazolidinone (2f), with 1 proceeded very smoothly in the presence of [PdCl2(dppf)] catalyst, giving N- benzyloxycarbonyl-4-(2,3-dimethyl-2,3-butanediolatoboryl)-L-phenylalanine benzyl ester (3a), N,N-dibenzyl-4-(2,3-dimethyl-2,3-butanediolatoboryl)-L- phenylalanine benzyl ester (3b), (4S)-3-benzyloxycarbonyl-4-[4-(2,3-dimethyl- 2,3-butanediolatoboryl)benzyl]-5-oxazolidinone (3c), and (4S)-3- butyloxycarbonyl-4-[4(2,3-dimethyl-2,3-butanediolatoboryl)benzyl]-5- oxazolidinone (3d), respectively, in high yields. Deprotection of 3a-d gave enantiomerically pure L-BPA in high total yields.

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

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An efficient and scalable strategy to prepare libraries of discrete conjugated oligomers (D = 1.0) using the combination of controlled polymerization and automated flash chromatography is reported. From this two-step process, a series of discrete conjugated materials from dimers to tetradecamers could be isolated in high yield with excellent structural control. Facile and scalable access to monodisperse libraries of different conjugated oligomers opens pathways to designer mixtures with precise composition and monomer sequence, allowing exquisite control over their physical, optical, and electronic properties.

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

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72287-26-4, Name is [1,1′-Bis(diphenylphosphino)ferrocene]dichloropalladium(II), belongs to catalyst-palladium compound, is a common compound. COA of Formula: C34H28Cl2FeP2PdIn an article, once mentioned the new application about 72287-26-4.

Pd-bis(azido) compounds [Pd(dppn)(N3)2] and [Pd(dppf)(N3)2], which contain bulky chelating bis(phosphine) ligands (dppn=1,8-bis(diphenylphosphino)naphthalene, dppf=1,1?-bis(diphenylphosphino)ferrocene), were prepared from the corresponding chlorides and NaN3. We also prepared the Pt-bis(azido) compound [Pt(1-dpn)(SMe2)(N3)2] containing a bulky monodentate phosphine (1-dpn=1-diphenylphosphino-naphthalene). All these compounds underwent [2+3] cycloaddition with isocyanides (R-NC, R=cyclohexyl, tert-butyl, 2,6-dimethylphenyl) to convert azido ligands to five-membered, C-coordinated tetrazolate rings. In addition, we observed the [Pd(dppn)Cl2]-mediated C-C coupling of PhC{triple bond, short}CH to generate the eta2-PhC{triple bond, short}C-C{triple bond, short}CPh ligand. All compounds have been structurally characterized by X-ray diffraction.

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

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Several palladium(II) complexes with 1,1?-bis(diphenylphosphino)octamethylferrocene (dppomf) and its oxidized form 1,1?-bis(diphenylphosphino)octamethylferrocenium (dppomf) have been synthesized and characterized by spectroscopic and electrochemical methods. For comparative purposes, analogous Pd(II) derivatives with 1,1?-bis(diphenylphosphino)ferrocene (dppf) have been also prepared. Single-crystal X-ray analyses have been carried out for the square-planar mononuclear compounds [Pd(H2O)2(dppf)](OTf)2 and [Pd(H2O)2(dppomf)](OTf)2 and for the binuclear complex [Pd(mu-OPF2O)(dppomf+)]2(BF4) 4·6CH2Cl2 in which two [Pd(dppomf+)]3+ moieties are held together by the oxygen atoms of two bridging PO2F2 groups derived from the oxidative degradation of PF6 ions. Selected dppf and dppomf Pd(II) complexes have been employed as catalyst precursors for the methoxycarbonylation of ethene (600 psi, 1:1 CO/C2H4, 85 C). It has been found that dppomf generates selective catalysts for the production of methyl propanoate, while dppf leads to a variety of low-molecular-weight oxygenates spanning from methyl propanoate to alternating oligoketones.

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

Brief introduction of [1,1′-Bis(diphenylphosphino)ferrocene]dichloropalladium(II)

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We report herein the preparation of ortho-vinylaryl S-trifluoromethylated sulfoximines through cross-coupling reactions. Two efficient palladium-catalyzed procedures (Stille and Suzuki) were developed, with use of ortho-iodo aryl sulfoximines as substrates, to give various vinyl derivatives in good yields. The difference in reactivity of the fluorinated derivatives, compared to nonfluorinated counterparts, allowed the use of free NH sulfoximines in the coupling processes, where they proved to be inert to cyclization. Finally, further transformations have been explored, such as metathesis coupling reactions, after post-functionalization of the nitrogen atom by another vinyl group.

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

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Complexes of 1,1′-bis(diphenylphosphino)ferrocene corresponding to the separate steps of cross-coupling have been identified and related to the catalytic cycle.

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

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We have synthesized biaryls from the coupling reaction between aryl sulfinates and aryl halides using homogeneous palladium catalytic system. The developed method is simple and efficient. These methodologies are particularly useful to prepare symmetrical as well as unsymmetrical biaryls with excellent product yield. The suggested protocol demonstrated a broad substrate scope.

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

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Reaction of lithium 1,3-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-1,3,2- diazaborol-2-ide with borane·THF provides the first boryl-substituted borohydride: lithium [1,3-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-1,3,2- diazaborol-2-yl]trihydroborate. The compound is fully characterized by 11B, 1H, and 7Li NMR spectra and other means, and these data are compared to neutral and anionic benchmark compounds. The compound crystallizes as a dimer complexed to four THF molecules. The dimer lacks the bridging B-H bonds seen in neutral boranes and is instead held together by ionic Li – -HB interactions. A preliminary scan of reactions with several iodides shows that the compound participates in an ionic reduction (with a primary-alkyl iodide), an organometallic reduction (Pd-catalyzed with an aryl iodide), and a radical reduction (AIBN-initiated with a sugar-derived iodide). Accordingly the new borylborohydride class may share properties of both traditional borohydrides and isoelectronic N-heterocyclic carbene boranes.

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

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A new [2.2]paracyclophane-based electron-rich and sterically bulky monophosphine ligand has been synthesized by an efficient and straightforward method. When combined with palladium, this ligand shows excellent performance in the Buchwald-Hartwig amination and Suzuki-Miyaura coupling reactions of various aryl chlorides. In both types of reactions, ortho-substituted, deactivated aryl chlorides are shown to be viable substrates. However, the Suzuki-Miyaura coupling appears to be easier, with palladium loading at 0.1 mol% being feasible. The Royal Society of Chemistry 2009.

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