Extracurricular laboratory:new discovery of Bis(dibenzylideneacetone)palladium

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Palladium(0)/PAr3-catalyzed intermolecular amination of C(sp3)-H bonds: Synthesis of beta-amino acids

An intermolecular C(sp3)-H amination using a Pd0/PAr3 catalyst was developed. The reaction begins with oxidative addition of R2N-OBz to a Pd0/PAr3 catalyst and subsequent cleavage of a C(sp3)-H bond by the generated Pd-NR2 intermediate. The catalytic cycle proceeds without the need for external oxidants in a similar manner to the extensively studied palladium(0)-catalyzed C-H arylation reactions. The electron-deficient triarylphosphine ligand is crucial for this C(sp3)-H amination reaction to occur.

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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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KINASE INHIBITORS

The present invention relates to compounds of formula I or a pharmaceutically acceptable salts thereof; wherein the variables R1-R5, Ar1, and X are as defined herein. The compounds are capable of modulating tyrosine kinase signal transduction in order to regulate, modulate and/or inhibit abnormal cell proliferation.

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

Simple exploration of Bis(dibenzylideneacetone)palladium

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PHOSPHORESCENT EMITTING COMPOSITIONS

A light emitting composition comprising a central platinum group transition metal and a bidentate ligand of novel structure for transition metal complexes forming a six membered ring. The platinum group transition metal may be selected from the group consisting of platinum, palladium, iridium, rhodium, ruthenium, and osmium. Additionally, OLED devices are disclosed, each of the OLED devices comprising a light emitting layer that includes one of the light emitting compositions.

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

Simple exploration of Bis(dibenzylideneacetone)palladium

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Homoallylic o-halobenzylamines: asymmetric diversity-oriented synthesis of benzo-fused cyclic amines

The presence of a halogen atom in the proximity of a homoallylic amine, obtained by asymmetric addition of allylzinc bromide to the corresponding tert-butyl sulfinimine, makes them versatile building blocks suitable to participate in several palladium-catalyzed processes, such as the intramolecular Heck reaction or the Sonogashira cross-coupling. The thus obtained ortho-alkynyl derivatives display two unsaturated functional groups which may be further modified by means of the intramolecular Pauson?Khand reaction or the ring-closing enyne metathesis. In this way, a variety of benzo-fused amines can be obtained in 2?3 steps from readily available starting materials.

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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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The metal complex used for the production of biphenyltetracarboxylic acid tetraester palladium (by machine translation)

[A] a high rate of reaction of dimethyl phthalate, 3, 3 ‘, 4, 4’ – biphenyltetracarboxylic acid ester ratio, catalyst and catalyst used for the production of high speed (TON) biphenyltetracarboxylic acid tetraester of. (2) Method using the following formula or its enantiomer compound as a catalyst [solution]. [Drawing] no (by machine translation)

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

New explortion of Bis(dibenzylideneacetone)palladium

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Monodentate Phosphorus Ligand-Enabled General Palladium-Catalyzed Allylic C-H Alkylation of Terminal Alkenes

Monodentate phosphorus ligands have been found to enable the palladium-catalyzed allylic C-H alkylation reaction of terminal alkenes with a wide variety of carbon nucleophiles. Moreover, an asymmetric allylic C-H alkylation of terminal alkenes with pyrazol-5-ones has been established in the presence of chiral phosphoramidite ligand and chiral phosphoric acid as co-catalyst. Mechanistic studies suggest that a ternary Pd(0) complex, coordinated with a monodentate phosphorus ligand, benzoquinone, and alkene, is most likely to be an active species.

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

Brief introduction of Bis(dibenzylideneacetone)palladium

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Palladium-Catalyzed Selective alpha-Alkenylation of Pyridylmethyl Ethers with Vinyl Bromides

An efficient palladium-catalyzed alpha-alkenylation of pyridylmethyl ethers with vinyl bromides is presented. A Pd/NIXANTPHOS-based catalyst system enables a mild and chemoselective coupling between a variety of pyridylmethyl ethers and vinyl bromides in good to excellent yields. Under the mild conditions, beta,gamma-unsaturated products are obtained without isomerization or Heck byproducts observed.

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

The important role of Bis(dibenzylideneacetone)palladium

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Substrate-Controlled Regio- and Stereoselective Synthesis of Boron-Substituted 1,4-Dienes via Copper-Catalyzed Boryl-Allylation of Alkynes with Allyl Phosphates and Bis(pinacolato)diboron

Boron-substituted 1,4-dienes are versatile building blocks for the synthesis of 1,4-dienes (skipped alkenes), a common motif in bioactive natural products, because of their utility in the Suzuki-Miyaura coupling reaction and conjugate additions. A method for the synthesis of boron-substituted 1,4-dienes by means of copper-catalyzed boryl-allylation of alkynes with allyl phosphate and bis(pinacolato)diboron has been developed. The regioselectivity with respect to the alkyne and allyl phosphate depends on the structures of both the alkyne and the allyl phosphate. For alkynes bearing at least one aryl substituent, addition of borylcopper to the alkyne mainly generates a beta-boryl-alpha-aryl-alpha-alkenylcopper species, whose subsequent reaction with secondary allyl phosphates provides gamma-(4E)-selective boron-substituted 1,4-dienes, and with primary allyl phosphates provided alpha-selective boron-substituted 1,4-dienes. On the other hand, the alpha-boryl-alpha-aryl-beta-alkenylcopper species formed as a minor intermediate from aryl alkyl acetylenes and the beta-borylalkenylcopper species formed from dialkyl acetylenes show poor regioselectivity with respect to the secondary allyl phosphate and produce a mixture of alpha- and gamma-selective boron-substituted 1,4-dienes. However, their reactions with the primary allyl phosphate are highly gamma-selective. For all of the alpha-selective reactions, the configuration of the C=C bond of the allyl phosphate was retained in the products. The palladium-catalyzed cross-coupling of boron-substituted 1,4-dienes and aromatic, alkenyl, and alkynyl halides gave polyenes or enynes in 68%-95% yield, demonstrating that these boron-substituted 1,4-dienes are versatile building blocks for the synthesis of 1,4-dienes.

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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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SPIRO-1,1′-BIINDANE-7,7-BISPHOSPHINE OXIDES AS HIGHLY ACTIVE SUPPORTING LIGANDS FOR PALLADIUM-CATALYZED ASYMMETRIC HECK REACTION

The present invention relates to catalyst complexes comprising palladium (Pd) and at least one spiro-1,1 ‘-biindane-7,7’- bisphosphine oxide ligand as disclosed herein, and their use. The present invention is further directed to the asymmetric Pd-catalyzed covalent carbon-carbon single bond formation from aryl, heteroaryl and alkenyl triflates and halides and olefins utilising the said catalyst complexes.

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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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A new tripod PPN bridging ligand and its copper, silver and palladium complexes: Syntheses, characterizations and X-ray structures

A new tripod bridging ligand 2-{bis(diisopropylphosphino)methyl}-1-methylimidazole, MeImCH(Pi-Pr2)2 (PPN) was synthesized conveniently by reacting 2-{bis(trimethylsilyl)methyl}-1- methylimidazole and chlorodiisopropylphosphine. The dicationic dinuclear complex [Cu2(PPN)2][CIO4]2 (1) was prepared by the reaction of the ligand with [Cu(MeCN)4]ClO4 in acetonitrile. The reaction of the ligand with AgNO3 in propane-2-ol followed by addition of NH4PF6 led to the formation of a similar type complex [Ag2(PPN)2][PF6]2 (2). The X-ray diffraction studies of 1 and 2 revealed a mu2-eta1:eta2 tripod-like bonding of the PPN ligand, with one P and one N atom chelating to one metal ion and the remaining one P atom binds to another metal ion, affording a face-to-face type molecule. An eight-membered M2P4C2 and a 10-membered M2P2N2C4 ring are thus formed with this new functional diphosphine ligand. In both complexes the two metal ions are held in very close proximity [2.6707 A? for 1 and 2.859(3) A? for 2]. Coplex 1 underwent a rapid ligand exchange process in solution. Besides these dinuclear complexes the ligand also afforded a mononuclear palladium complex, [PdCl2(PPN)] (3), when it was treated with an equimolar amount of [PdCl2(PhCN)2] in benzene. In 3 the ligand acts as a bidentate chelate through its two phosphorus atoms, leaving the imidazole donor dangling. On the other hand, a P,P-bridged dinuclear Pd(I) complex [Pd2Cl2(PPN)2] (4) was achieved by reacting two moles of the ligand with one mole of [PdCl2(PhCN)2], followed by the addition of one mole of Pd(dba)2 [dba = dibenzylideneacetone].

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