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Palladium-catalyzed carbonylation of benzylic ammonium salts to amides and esters: Via C-N bond activation

An efficient palladium-catalyzed carbonylation reaction of readily available quaternary ammonium salts with CO is reported for the first time to afford arylacetamides and arylacetic acid esters via benzylic C-N bond cleavage. This protocol features mild reaction conditions under atmospheric pressure of CO, a redox-neutral process without an additional oxidant, and a broad substrate scope for various kinds of amines, alcohols and phenols.

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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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Di([5]trovacenyl)ethyne, di([5]trovacenyl)butadiyne, and di-1,4-([5]trovacenylethynyl)benzene: Electrocommunication and magnetocommunication mediated by -C?C-, -C?C-C?C- and -C?C-C6H4-C?C- spacers

The synthesis of dinuclear derivatives of trovacene (eta7- C7H7)V(eta5-C5H5) (V) is reported, in which ethynyl (6..), butadiynyl (7..), and 1,4-di(ethynyl)phenyl (8..) groups serve as spacers between paramagnetic (S = 1/2) [5]trovacenyl units. The mononuclear precursors [5]trovacenylcarbaldehyde (2.) and [5]trovacenylacetylene (4 .) are also described. Structural characterization by X-ray diffraction has been performed for 4., 6.., 7 .., and 8… Electronic communication as gleaned from cyclic voltammetry only manifests itself in the reduction processes where redox splitting deltaE1/2(0/1-, 1-/2-) is resolved for 6.. (deltaE1/2 = 150 mV) and indicated for 7.. (deltaE1/2 ? 80 mV). Magnetocommunication leads to exchange coupling of the two electron spins which reside in vanadium centered orbitals. The values JEPR(6..) = (-)0.92, JEPR(7 ..) = (-)0.56, and JEPR(8..) = (-)0.005 cm -1 are derived from the 51V hyperfine patterns. Accordingly, attenuation of exchange interaction by oligoalkyne spacers is weak, corresponding to a factor of 0.6 only per added -C?C- unit. In the determination of very weak long distance exchange interactions, EPR excels because of the range 5 ¡Á 10-4 ? J ? 1.5 cm -1 accessible in the case of 51V as a reporting magnetic nucleus and because competing intermolecular exchange is quenched in dilute fluid solution. This is demonstrated by the value Jchi(7 ..) = -3.84 cm-1 obtained from a magnetic susceptibility study, which exceeds JEPR(7..) by a factor of 7. The small magnitude of spin exchange interaction between trovacene units reflects the fact that the spin bearing V3dz2 orbital is virtually orthogonal to the pi-perimeter ligand orbitals and weakly overlapping only with the a 1g(sigma) ring orbitals, creating two bottlenecks for spin-exchange in the spacer-containing ditrovacenes.

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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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Palladium-Catalyzed Intramolecular Self-Alkylation of Polyfluoroarene via Heck and Decarboxylation Process

An efficient palladium-catalyzed cyclization and polyfluorophenylation of gamma,delta-unsaturated polyfluorobenzoyl oxime ester via iminopalladation/polyfluorobenzoyloxy decarboxylation cascade reaction is developed. The protocol provides a practical and atom-economical access to a broad scope of various polyfluorophenylated dihydropyrrole derivatives. The reaction effectively utilizes the polyfluorobenzoyloxy leaving group as polyfluorophenylated source for the first time, precluding the need of additional polyfluoroarene. This is the first example of the introduction of electron-deficient arenes in the further transformation of Narasaka-Heck-type reaction. Additionally, the reaction is conducted in a short time.

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

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

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AMIDE COMPOUNDS, COMPOSITIONS AND APPLICATIONS THEREOF

The present disclosure relates to substituted amide compounds that are inhibitors of Fatty Acid Amide Hydrolase (FAAH), their stereoisomers, tautomers, prodrugs, polymorphs, solvates, pharmaceutically acceptable salts, and pharmaceutical compositions containing them. These compounds are useful in the treatment, prevention, prophylaxis, management, or adjunct treatment of all medical conditions related to inhibition of Fatty Acid Amide Hydrolase (FAAH), such as pain including acute and post operative pain, chronic pain, cancer pain, cancer chemotherapy induced pain, neuropathic pain, nociceptive pain, inflammatory pain, back pain, pain due to disease of various origin such as: diabetic neuropathy, neurotropic viral disease including human immunodeficient virus (HIV), herpes zoster such as post herpetic neuralgia; polyneuropathy, neurotoxicity, mechanical nerve injury, carpal tunnel syndrome, immunologic mechanisms like multiple sclerosis; sleep disorders, anxiety and depression disorders, inflammatory disorders, weight and eating disorders, Parkinson’s disease, addiction, spasticity, hypertension or other disorders. The disclosure also relates to the process of preparation of the amide compounds. The present disclosure also relates to methods for the preparation of such compounds, and to pharmaceutical compositions containing them.

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

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Convenient synthesis of 1H-indol-1-yl boronates via palladium(0)-catalyzed borylation of bromo-1H-indoles with ‘pinacolborane’

An atom-economic Pd0-catalyzed synthesis of a series of pinacol-type indolylboronates 3 from the corresponding bromoindole substrates 2 and pinacolborane (pinBH) as borylating agent was elaborated. The optimal catalyst system consisted of a 1:2 mixture of [Pd(OAc)2] and the ortho-substituted biphenylphosphine ligand L-3 (Scheme 4, Table). Our synthetic protocol was applied to the fast, preparative-scale synthesis of 1-substituted indolylboronates 3a-h in the presence of different functional groups, and at a catalyst load of only 1 mol-% of Pd.

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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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Scope of Palladium-Catalyzed Alkylative Ring Opening

We have explored the scope of the palladium-catalyzed nucleophilic ring opening methodology. New highly selective and highly active catalysts have been found for the ring opening of oxabenzonorbornadienes. Employing these catalysts, the addition of various alkyl nucleophiles to oxabenzonorbornadiene has been achieved. In addition, reaction of diethylzinc with [3.2.1] oxabicyclic alkenes has been accomplished to yield ring-opened products as well as functionalized alkene addition products.

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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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Synthesis and Properties of Ethene-Bridged Terthiophenes

A method for the facile synthesis of ethene-bridged terthiophenes (EBTTs) in two steps has been developed. The first step is a double Sonogashira coupling between 3?,4?-dibromo-2,2?:5?,2?-terthiophene and terminal alkynes to give dialkynylated terthiophenes, and the second step is a cyclization reaction to afford EBTTs. The fundamental physical properties of EBTTs were also studied.

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

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Oxidative Mechanochemistry: Direct, Room-Temperature, Solvent-Free Conversion of Palladium and Gold Metals into Soluble Salts and Coordination Complexes

Noble metals are valued, critical elements whose chemical activation or recycling is challenging, and traditionally requires high temperatures, strong acids or bases, or aggressive complexation agents. By using elementary palladium and gold, demonstrated here is the use of mechanochemistry for noble-metal activation and recycling by mild, clean, solvent-free, and room-temperature chemistry. The process leads to direct, efficient, one-pot conversion of the metals, including spent catalysts, into either simple water-soluble salts or metal?organic catalysts.

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

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Handy Protocols using Vinyl Nosylates in Suzuki-Miyaura Cross-Coupling Reactions

Vinyl nosylates derived from 1,3-dicarbonyl compounds could be engaged in Suzuki-Myaura cross coupling reactions with aryl-, vinyl- and methylboronic acids or trifluoborate derivatives at room temperature in the presence of 2mol% of [1,1?-bis(diphenylphosphino)ferrocene]dichloropalladium(II) [PdCl2(dppf)]. One-pot procedures have been set up for practical and efficient nosylation-cross-coupling reactions. Nosylate, as a cheap novel pseudo-halide, gives very stable compounds and is very efficient in Suzuki-Myaura cross coupling reactions (21 examples, 44-99%).

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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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Synthesis, X-ray, spectroscopic and a preliminary Suzuki coupling screening studies of a complete series of dppfMX2 (M=Pt, Pd; X=Cl, Br, I)

A complete series of dppfMX2 (M=Pt, Pd; X=Cl, Br, I) compounds have been synthesized using different routes, and characterized fully. The synthesis of dppfPdI2 has been achieved by reacting Pd(COD)Cl2 with dppf in the presence of NaI. X-ray structures of dppfPdBr2 and dppfPdI2 have also been reported for the first time in this study. A preliminary Suzuki coupling screening study reveals that dppfPdX2 compounds are superior to the conventional Ph3P-based catalysts and bidentate phosphine-based ligands. Reactions carried out under in situ conditions also gave a similar trend, but their respective activities were much lower than that of the fully formed catalysts.

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