Extracurricular laboratory:new discovery of Bis(tri-tert-butylphosphine)palladium

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P-C Bond Activation and eta4-Coordination of Arene: X-ray Crystal Structure of a Dinuclear mu-Phosphido mu-eta2:eta2-Phenoxo Zwitterionic Complex of Palladium Trapping an Aggregate of Three Hydrogen-Bonded Phenol Molecules

Pd2 reacts photochemically with an excess of phenol in n-hexane to give the dinuclear complex <2Pd2(mu-eta2:eta2-C6H5O)>*3C6H5OH (1); X-ray crystallography shows a linear chain of three phenol molecules hydrogen-bonded to the phenoxide ligand which is eta4-coordinated to the Pd2 framework.The ? coordination of the phenoxide ring is retained in solution, as evidenced by 1H-NMR spectroscopy.

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

Archives for Chemistry Experiments of Bis(dibenzylideneacetone)palladium

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Enantioselective palladium(0)-catalyzed intramolecular cyclopropane functionalization: access to dihydroquinolones, dihydroisoquinolones and the BMS-791325 ring system

Taddol-based phosphoramidite ligands enable enantioselective palladium(0)-catalyzed C-H arylation of cyclopropanes. The cyclized products are obtained in high yields and enantioselectivities. The reported method provides efficient access to a broad range of synthetically attractive cyclopropyl containing dihydroquinolones and dihydroisoquinolones as well as allows for an efficient enantioselective construction of the 7-membered ring of the cyclopropyl indolobenzazepine core of BMS-791325.

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

Discovery of Bis(dibenzylideneacetone)palladium

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Desymmetrization of cyclic olefins via asymmetric Heck reaction and hydroarylation

An asymmetric Heck reaction allows desymmetrization of substituted cyclic olefins in high dr and ee. A bisphosphine oxide is uniquely stereoselective for this purpose. Desymmetrization of bicyclic olefins via hydroarylation can also be realized in high ee.

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

A new application about 32005-36-0

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Pd-Catalyzed Decarbonylative Cross-Couplings of Aroyl Chlorides

This report describes a method for Pd-catalyzed decarbonylative cross-coupling that enables the conversion of carboxylic acid derivatives to biaryls, aryl amines, aryl ethers, aryl sulfides, aryl boronate esters, and trifluoromethylated arenes. The success of this transformation leverages the Pd0/Brettphos-catalyzed decarbonylative chlorination of aroyl chlorides, which can then participate in diverse cross-coupling reactions in situ using the same Pd catalyst.

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

Awesome Chemistry Experiments For Bis(dibenzylideneacetone)palladium

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Derisking the Cu-Mediated 18F-Fluorination of Heterocyclic Positron Emission Tomography Radioligands

Molecules labeled with fluorine-18 (18F) are used in positron emission tomography to visualize, characterize and measure biological processes in the body. Despite recent advances in the incorporation of 18F onto arenes, the development of general and efficient approaches to label radioligands necessary for drug discovery programs remains a significant task. This full account describes a derisking approach toward the radiosynthesis of heterocyclic positron emission tomography (PET) radioligands using the copper-mediated 18F-fluorination of aryl boron reagents with 18F-fluoride as a model reaction. This approach is based on a study examining how the presence of heterocycles commonly used in drug development affects the efficiency of 18F-fluorination for a representative aryl boron reagent, and on the labeling of more than 50 (hetero)aryl boronic esters. This set of data allows for the application of this derisking strategy to the successful radiosynthesis of seven structurally complex pharmaceutically relevant heterocycle-containing molecules.

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

Simple exploration of 32005-36-0

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Palladium complex catalyzed acylation of allylic esters with acylsilanes

Acylation of allylic esters (2) with acylsilanes (1) in the presence of a catalytic amount (5 mol %) of a palladium complex is reported. The reaction proceeds selectively to afford beta, gamma-unsaturated ketones (3) in high yields. [Pd(eta3-C6H5CH=CHCH2)(CF 3COO)]2 (4a) showed the best catalytic activity. After the reaction, formation of CF3COOSiMe3 (5a) was confirmed by 29Si NMR measurement of the resulting reaction mixture, indicating the trimethylsilyl moiety effectively traps the CF3COO leaving group from 2. The leaving group of the allylic esters affects the reaction considerably: allylic trifluoroacetate gave the best result, while the corresponding acetates and trichloroacetates did not afford any acylation products at all. Stoichiometric reaction of 4a with 1 gave acylation product 3 with a formation of 5a and Pd(0), whereas no acylation reaction took place with the corresponding acetate complex [Pdeta3-C6H5CH=CHCH2)(CH 3COO)]2 (4b). A DFT calculation suggests that interaction of high-lying HOMO of 1 and low-lying LUMO of eta3-allylpalladium trifluoroacetate intermediate 4 would be indispensable in the catalytic cycle.

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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(tri-tert-butylphosphine)palladium

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Directly Observed Reductive Elimination of Aryl Halides from Monomeric Arylpalladium(II) Halide Complexes

Monomeric, three-coordinate arylpalladium(II) halide complexes undergo reductive elimination of aryl halide to form free haloarene and Pd(0). Reductive elimination of aryl chlorides, bromides, and iodides were observed upon the addition of P(t-Bu)3 to Pd[P(t-Bu)3](Ar)(X) (X = Cl, Br, I). Conditions to observe the equilibrium between reductive elimination and oxidative addition were established with five haloarenes. Reductive elimination of aryl chloride was most favored thermodynamically, and elimination of aryl iodide was the least favored. However, reductive elimination from the aryl chloride complex was the slowest, and reductive elimination from the aryl bromide complex was the fastest. These data show that the electronic properties of the halide, not the thermodynamic driving force for the addition of elimination reaction, control the rates for addition and elimination of haloarenes. Mechanistic data suggest that reversible reductive elimination of aryl bromide to form Pd[P(t-Bu)3] and free aryl bromide is followed by rate-limiting coordination of P(t-Bu)3 to form Pd[P(t-Bu)3]2. Copyright

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

Discovery of 53199-31-8

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Host-guest behavior of a heavy-atom heterocycle Re4(CO)16(mu-SbPh2)2(mu-H)2 obtained from a palladium-assisted ring opening dimerization of Re2(CO)8(mu-SbPh2)(mu-H)

The heavy-atom heterocycle Pd[Re2(CO)8(mu-SbPh2)(mu-H)]2 (5) has been synthesized by the palladium-catalyzed ring-opening cyclodimerization of the three-membered heterocycle Re2(CO)8(mu-SbPh2)(mu-H) (3). The Pd atom occupies the center of the ring. The Pd atom in 5 can be removed reversibly to yield the palladium-free heterocycle [Re2(CO)8((mu-SbPh2)(mu-H)]2 (6).

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

Archives for Chemistry Experiments of 53199-31-8

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Palladium-Assisted “Aromatic Metamorphosis” of Dibenzothiophenes into Triphenylenes

Abstract Two new palladium-catalyzed reactions of aromatic sulfur compounds enabled the conversion of dibenzothiophenes into triphenylenes in four steps. This transformation of one aromatic framework into another consists of 1) 4-chlorobutylation of the dibenzothiophene to form the corresponding sulfonium salt, 2) palladium-catalyzed arylative ring opening of the sulfonium salt with a sodium tetraarylborate, 3) an intramolecular SN2 reaction to form a teraryl sulfonium salt, and 4) palladium-catalyzed intramolecular C-S/C-H coupling through electrophilic palladation. Symmetrical as well as unsymmetrical triphenylenes of interest were synthesized in a tailor-made fashion in satisfactory overall yields. A change of heart: The invention of two palladium-catalyzed arylation reactions of organosulfur compounds enabled the transformation of dibenzothiophenes into triphenylenes and thus a fundamental change in the core aromatic structure (see scheme). Both symmetrical and unsymmetrical triphenylenes were synthesized in a tailor-made fashion in satisfactory overall yield.

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

Final Thoughts on Chemistry for Bis(tri-tert-butylphosphine)palladium

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Heck coupling of haloaromatics with octavinylsilsesquioxane: Solution processable nanocomposites for application in electroluminescent devices

A new solution processable nanocomposite material has been prepared via the Heck coupling of octavinylsilsesquioxane with a selected bromoaromatic hole transport compound. Resultant electroluminescent devices show an 18% improvement in external quantum efficiencies over their small molecule analogues. The Royal Society of Chemistry 2005.

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