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Unexpected ortho-Heck Reaction under the Catellani Conditions

An unexpected ortho-Heck reaction has been discovered during the study of palladium/norbornene (Pd/NBE) catalysis. Under the Catellani reaction conditions in the presence of lithium salts and olefins, Heck coupling takes place at the ortho position instead of the commonly observed ipso position; meanwhile, a norbornyl group is introduced at the arene ipso position. Systematic deuterium labeling and crossover experiments suggest an unusual 1,4-palladium migration/intramolecular hydrogen transfer pathway. The knowledge gained in this study could provide insights for the future development of the Pd/NBE catalysis.

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

Awesome and Easy Science Experiments about Bis(dibenzylideneacetone)palladium

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Synthesis and reactivity of aryl- and alkyl-palladium(II) complexes with functional phosphines and phosphinoenolate ligands: First analogues of model nickel catalysts

Phenyl- and methyl-palladium(II) complexes analogous to model nickel(II) catalysts were prepared from readily available precursors. The methods used allow different ligands to be introduced in the co-ordination sphere. For example, the chelating phosphinoenolate ligand in [PdPh{Ph2PCH-..C(-..O)NPh2}L 2] [L2 = Ph2PCH2C(O)NPh2] was displaced by 1 equivalent of Ph2PCH2C(O)Ph(L1) to give [PdPh{Ph2PCH-..C(-..O)Ph}L2] whereas the terminal functional phosphine was displaced by P(C6H11)3 to give [PdPh{Ph2PCH-..C(-..O)NPh2}{P(C 6H11)3}]. Owing to favourable ligand-redistribution reactions, treatment of a mixture of complexes trans-[PdMe(Cl)L22], trans-[PdMe(Cl)L12] and trans-[PdMe(Cl)L1(L2)] (which cannot be isolated pure) with an excess of NaOMe in toluene selectively afforded the phosphinoenolate complex [PdMe{Ph2PCH-..C(-..)Ph}L2]. The enolate moiety of [PdPh{Ph2PCH-..C(-..O)NPh2}L 2] and of [PdMe{Ph2PCH-..C(-..O)NPh2}L 2] reacted with R?N=C=O (R? = Ph or p-tolyl) with formation of a carbon-carbon bond in a Michael-type addition and the products were shown to exist in the form of two isomers a and b, characterised by a N-H … O or a N-H … N hydrogen bond within the ligand system. Insertion of CO into the Pd-Me bond of [PdMe{Ph2PCH-..C(-..O)NPh2}L 2] or [PdMe{Ph2C[=C(O)NHPh]C(O)NPh2}L2] yielded the corresponding acyl complexes. Although [PdMe{Ph2PCH-..C(-..O)Ph}(PPh3)] inserted ethylene into its Pd-Me bond, as evidenced by quantitative formation of propylene, the palladium hydride that must be generated by the beta-elimination reaction decomposes before further ethylene insertion can 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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METHOD FOR PREPARING DELTA-LACTONES

The present invention relates to methods of forming delta-lactone compounds by reaction of a diene with carbon dioxide in the presence of Pd and a phosphine ligand.

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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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Insertion of platinum and palladium into a sulfur(IV)-sulfur(II) bond of a sulfur-substituted sulfurane

Transition metal complexes are known to react with disulfides and insert into the disulfide bond, but there has been no report on similar reactivity towards the hypervalent sulfur(IV)-sulfur(II) bond compound, a sulfur-substituted sulfurane, because of its instability. In this paper, we report the reactions of the sulfur-substituted sulfurane 1 with platinum and palladium complexes, in which the corresponding complexes 2 and 3 with an O,S,S?-ligand were obtained by bond cleavage of both the sulfur(IV)-sulfur(II) bond and the sulfur(IV)-oxygen bond. The structures of the complexes were characterized by NMR spectroscopic studies, elemental analysis, and X-ray crystallographic analysis. The palladium complex 3 underwent elimination of triphenylethylene episulfide when treated with dppe to give the dppe palladium complex 4 with an O,S-ligand, which was also obtained by the reaction of Pd(dba)2 and dppe with the sulfurane 1. X-ray crystallographic analysis of complexes 2 and 4 revealed a square-planar structure around the platinum or palladium. The formation mechanisms of these complexes 2-4 are discussed. The Royal Society of Chemistry.

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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, sequential, three-component cross-coupling of aryl halides, alkynes, and arynes

(Chemical Equation Presented) Three’s a crowd? Polycyclic aromatic hydrocarbons can be synthesized efficiently and in high yield using the first palladium-catalyzed, sequential, three-component coupling of alkynes and arynes with aryl halides (see scheme). This process appears to involve the catalytic, stepwise carbopalladation of an alkyne and an aryne to generate the three-component 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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Diazadiene als Steuerliganden in der homogenen Katalyse XIII. Cocyclotetramerisierung zweier verschiedener Alkine ueber ein Palladacyclopentadien zu einem Cyclooctatetraen

The reaction of bis(dibenzylideneacetone)palladium with N-arylazadienes (dad =ArN=CR’CR’=NAr) in the presence of dialkylacetylene dicarboxylate V gives the dad-stabilized palladacyclopentadiene I.This complex is a precatalyst for the cyclotrimerization of V and other alkynes.With 3-methyl-1-butyne-3-ol IV and the diester V a 1/2-cyclotrimer is formed catalytically, which contains a gamma-lactone ring resulting from intramolecular transesterification.No mellitic acid ester was formed in this experiment, nor was it formed in an analogous reaction with 1-trimethylsilyl-1-propyne-3-ol IX and V, which gave the corresponding 2(3H)-benzofuranone X (75percent) together with a second product XI (25percent).XI is a 1/3 cocyclotetramer of IX and V, again with a lactone ring fused to the cyclooctatetraene.XI is the first octa-substituted cyclooctatetraene formed catalytically from two different alkynes.

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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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Design, synthesis and application of triazole ligands in suzuki miyaura cross coupling reaction of aryl chlorides

DFT calculations have been demonstrated to be a valuable tool for the mechanistic study of reaction which is difficult to acquire from pure experimental techniques. Structural, electronic and coordination aspects of synthesized triazole ligands were investigated theoretically by structure optimization on Gaussian 09 package by DFT approach at B3LYP/6-31G (d, p). HOMO-LUMO energy gaps correlated to its chemical reactivity and this information applied to interpret the role of ligand in the formation of ligand-metal complex. Electron rich environment around the triazole core stabilized the HOMO orbital and made these electrons available to form complex with Pd centre. The DFT calculations provide a plausible mechanism for the reaction that is consistent with the available experimental facts. A series of triazole ligands have been synthesized via efficient 1,3-dipolar cycloaddition of readily available azide and alkynes for coordination to Pd centre. Characterization of all the synthesized compounds was done by FTIR, 1H NMR, 13C NMR and HRMS. Their ligand-Pd complexes provided excellent yields in the Suzuki-Miyaura coupling reactions (up to 92% yield) of unactivated aryl chlorides. Ligand 4-(2,6-dimethoxyphenyl)-1-phenyl-1H-1,2,3-triazole (L2) was found to be most effective ligand because of electron donating 2,6 dimethoxy phenyl moiety attached to triazole ring at 4-position that facilitated the formation of electron rich ligand-catalyst complex. The complex favoured the oxidative addition step of Pd across the aryl chloride substrate and thus allowed for the development of highly active ligand-catalyst system for Suzuki reaction. During computational analysis, 4-(2,6-dimethoxyphenyl)-1-phenyl-1H-1,2,3-triazole (L2) also showed lowest band gap due to electron rich distribution pattern on the HOMO that are involve in ligand-Pd complex formation. Conclusively, these triazoles ligands were found to be more competent and attractive for palladium catalyst because of simplistic pathway for the synthesis of triazole motif and the ease of individual tuning of the substituents on triazole core or exocyclic to it.

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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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2-ACYLAMINOBENZAMIDE DERIVATIVES AND PREVENTIVE AND REMEDY FOR DISEASES CAUSED BY THE SUPERMULTIPLICATION OF VASCULAR INTIMAL CELLS

The present invention relates to 2-acylaminobenzamide derivatives represented by the general formula: wherein R1, R2, R3, R4and R5represent each a hydrogen atom etc.; X represents a vinylene group etc.; B represents a group represented by the general formula: -N(R6)(R7)wherein R6and R7represent each a hydrogen atom etc., a group represented by the general formula: -NH-(CH2)n-A-R8wherein A represents a single bond etc.; R8represents a hydroxy group etc. or a hydroxyamino group which are useful as agents for the prevention and treatment of diseases caused by excessive proliferation of vascular intimal cells.

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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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Unusual palladium-catalyzed silaboration of allenes using organic iodides as initiators: Mechanism and application

A highly regio- and stereoselective method for the synthesis of various 2-silylallylboronates 7 from allenes 1 and 2-(dimethylphenylsilanyl)-4,4,5,5- tetramethyl[1,3,2]dioxaborolane (5) catalyzed by palladium complexes and initiated by organic iodides is described. Treatment of monosubstituted aryl and alkylallenes RCH=C=CH2 (1a-m) and 1,1-dimethylallene (1n) with borylsilane 5 in the presence of Pd-(dba)2 (5 mol %) and organic iodide 3a (10 mol %) afforded the corresponding silaboration products 7a-n in moderate to excellent yields. This catalytic silaboration is totally regioselective with the silyl group of 5 adding to the central carbon and the boryl group to the unsubstituted terminal carbon of allene. Furthermore, the reactions show very high Estereoselectivity with the Z/E ratios lying in the range from 1/99 to 7/93. In the absence of an organic iodide, silaboration of 1 with 5 still proceeds, but gives products having completely different regiochemistry as that of 7. The silaboration chemistry can be applied to the synthesis of homoallylic alcohols. Treatment of allenes (1) with borylsilane 5 and aldehydes 14 in the presence of Pd(dba)2 (5 mol %) and 3a (10 mol %) at 80C in ethyl acetate for 5 h afforded homoallylic alcohols 15a-p in one pot in good to excellent yields, with exceedingly high syn selectivity (>93%). Mechanistic pathways involving an unusual palladium-catalyzed three-component assembling reaction of dimethylphenylsilyl iodide, allene 1, and borylsilane 5 were proposed to account for these catalytic reactions.

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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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Sequential silylcarbocyclization/silicon-based cross-coupling reactions

A sequential rhodium-catalyzed silylcarbocyclization of enynes parlayed with a palladium-catalyzed, silicon-based cross-coupling reaction has been developed for the synthesis of highly substituted cyclopentanes. 1,6-Enynes reacted with benzyldimethylsilane in the presence of rhodium catalysts to afford five-membered rings bearing a (Z)-alkylidenylbenzylsilyl group. A variety of substitution patterns and heteroatom substituents were compatible. The silylcarbocyclization in which an unsaturated ester participated was also achieved. The resulting alkylidenylsilanes underwent palladium-catalyzed cross-coupling using tetra-n-butylammonium fluoride. This cross-coupling reaction displayed a broad substrate scope. A wide variety of substitution patterns, electronic properties, and heteroatoms were compatible. All of the cross-coupling reactions proceeded in high yields under very mild conditions and with complete retention of double bond configuration, resulting in densely functionalized 3-(Z)-benzylidenecyclopentanes and heterocycles.

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