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(Chemical Equation Presented) The direct approach: Tandem cyclization of 1-aryl-4-aza-2-bromo-1-alken-6-ynes with catalytic Pd(OAc)2 and cesium carbonate in EtOH led to direct construction of tri- or tetracyclic heterocycles, through intramolecular carbopalladation and aromatic C-H bond functionalization (see scheme). This route in which two C-C bonds are formed enables the construction of complex heterocyclic skeletons directly from readily prepared enynes.

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

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Diamidophosphite ligands based on 1,1?-bis(hydroxymethyl)ferrocene or N1,N2-bis((S)-1-hydroxy-3,3-dimethylbutan-2-yl)oxalamide and bearing 1,3,2-diazaphospholidine rings with stereogenic phosphorus atoms were obtained. The use of these ligands provides up to 96% ee in Pd-catalyzed asymmetric allylations of (E)-1,3-diphenylallyl acetate, up to 70% ee in Pd-catalyzed desymmetrizations of N,N?-ditosyl-meso-cyclopent-4-ene-1,3- diol bis-carbamate and up to 80% ee in Pd-catalyzed allylic alkylations of cinnamyl acetate with ethyl 2-oxocyclohexane-1-carboxylate. Results obtained with a diamidophosphite containing an oxalamide framework show the considerable potential of such ligands in enantioselective catalysis.

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

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The invention provides an antimycobacterial 6-aryl-9-(m- or p-substituted-benzyl) purine and purine analog compounds.

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

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Dihydropyrans and dihydrofurans bearing an aryl substituent in the 2-position are regio- and stereoselectively synthesized by Heck arylation of cyclic enol ethers with aryldiazonium salts.

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

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Enyne cycloisomerizations can provide an efficient means for forming carbon-carbon bonds. We describe stereoselectively dichotomous enyne cycloisomerizations, entirely dependent on the selection of catalytic manifold. Ruthenium catalysis provides trans-fused bicyclic systems, whereas palladium catalysis provides the analogous cis-fused bicycles. A number of substrates are investigated, and the outcomes ultimately offer a clear mechanistic rationale for these observations. Copyright

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

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In homogeneous catalysis, the catalyst is in the same phase as the reactant. The number of collisions between reactants and catalyst is at a maximum.In a patent, 52522-40-4, name is Tris(dibenzylideneacetone)dipalladium-chloroform, introducing its new discovery. Safety of Tris(dibenzylideneacetone)dipalladium-chloroform

A series of organometallic chiral complexes of palladium containing the chelate Duphos, l, 2-bis[(2/?, 5/?)-2, 5-dimethylphospholanyljbenzene 1, have been prepared. These include the 1, 3-diphenylallyl cationic compound, [Pd(PhCHCHCHPh)(l)][CF3S03] 2, the palladium(O) fumaronitrile complex [Pd(NCCH=CHCN)(l)] 3, and the pentafluorophenyl derivatives [Pd(R)(C6F5)(l)] (R = Me 4a, Et 4b, or Bu 4c). The solid-state structures of 2 and 4a have been determined by X-ray diffraction. The structure of complex 4a deviates markedly from the expected square planar geometry. Duphos 1 affords a ca. 98% enantiomeric excess in the enantioselective allylic alkylation reaction of a 1, 3-diphenylallyl precursor. Detailed ‘H and 13C NMR results are reported. The Royal Society of Chemistry 2000.

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

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This report details a palladium-catalyzed process to access highly functionalized, optically active allylic aryl ethers. A number of electron-deficient alkenyl triflates underwent enantioselective and site-selective coupling with acyclic aryl enol ethers in the presence of a chiral palladium catalyst. This transform provides chiral allylic ether products in high yields and excellent enantiomeric ratios, furnishing a unique disconnection to incorporate heteroatoms at a stereocenter. Finally, the applicability of the products to target synthesis was demonstrated through the formation of a chiral allylic alcohol and the generation of a flavone-inspired product.

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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 iridium-catalyzed site-selective C-H borylation of 2-pyridones has been developed. The site selectivity is predominantly controlled by steric factors, and we can access C4, C5, and C6 C-H on the 2-pyridone ring by the judicious choice of ligand and solvent. Subsequent Suzuki-Miyaura cross-coupling of the borylated products also proceeds to form the corresponding arylated pyridones in good overall 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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Herein we report the first palladium(0)-catalyzed asymmetric allylic alkylation (AAA) of allyl enol ether via pi-allylpalladium intermediate using Trost chiral diphosphine. This unprecedented reaction produced very rare alpha-aryl quaternary aldehydes with multi-functional groups. The main novelty in the chemistry demonstrates that enol ethers can be used as precursors for pi-allylpalladium intermediates, an observation that is certainly rare and to the best of our knowledge, perhaps without prior precedent. Chiral ligand (R,R)-L3 was found to be optimal in this Pd-AAA reaction and provided good to excellent yield (80?95%) and enantioselectivity (70?90%) with a range of analogs.

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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 Pd-catalyzed highly regioselective 1,2-difunctionalization of vinylarenes is disclosed in which multisubstituted olefins are efficiently and conveniently constructed under ambient temperature with good compatibility and a broad substrate scope. Notably, a quarternary carbon center could be readily built up from 1,1-disubstituted styrenes, which are big challenges in the previous methods.

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