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Several Pd(0) complexes catalyze the dimerization of Mes*PCNPh [2, Mes* = 2,4,6-(t-Bu)3C6H2] to the unsymmetrical heterocycle Mes*P(mu-CNPh)NPh(mu-CPMes*) (5). The symmetrical dimer [Mes*P(mu-CNPh)]2 (7), which forms slowly by uncatalyzed dimerization of 2, does not interconvert with 5; both 5 and 7 were structurally characterized by X-ray crystallography. The Pt complexes PtL2[eta2-(P,C)-Mes*PCNPh] [8, L = 1/2 dppe (Ph2PCH2-CH2PPh2); 9, L = PPh3; 10, L = PCy3 (Cy = c-C6H11)], models for intermediates in the catalysis, were prepared. Isomerization of Mes*PCCPh2 (3) to the phosphaindan [2,4-(t-Bu)2C6H2(G-CMe2CH 2PCH=CPh2)] (6), which we previously observed with Rh(I) catalysts, is catalyzed by Pt(PCy3)2 or the known Pt(PPh3)2[eta2-(P,C)-Mes*PCCPh2] (12). Comparison of the metal-mediated reactions of 2 and 3 suggests that the initial steps in the catalyses, coordination of the phosphacumulene to M(0), followed by loss of a ligand, are similar.

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

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Chloroacyl halides are obtained under mild conditions by catalytic carbonylation in halogenated solvents of allylic halides or ethylene and allyl chloride mixtures under pressure of CO and anhydrous HCl in the presence of PdCl2; excellent selectivities for dichloroacyl and chloroacyl derivatives are achieved. Allyl chloride is partly consumed for the regeneration of palladium chloride. The product of oxidative addition of HCl to the oligomeric [Pd(CO)Cl](n) formed in situ by reaction of CO on PdCl2 is proposed as the first step towards the generation of the active species.

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

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There are disclosed compounds that modulate or inhibit the enzymatic activity of indoleamine 2,3-dioxygenase (IDO), pharmaceutical compositions containing said compounds and methods of treating proliferative disorders, such as cancer, viral infections and/or inflammatory disorders utilizing the compounds of the invention.

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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 present invention provides compounds of formula (I): their pharmaceutically acceptable salts or esters, enantiomeric forms, diastereoisomers and racemates, the preparation of the above-mentioned compounds, pharmaceutical compositions containing them and their manufacture, as well as the use of the above-mentioned compounds in the control or prevention of illnesses such as cancer.

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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 copper-catalyzed gamma-selective and stereospecific substitution reaction of allylic carbonates with a diboron reagent affording allylboron compounds is described. Boryl group was selectively introduced at the gamma-position of the leaving carbonate group. Functionalized allylboronates that have an acetal, ester, or isolated alkene were prepared. The reaction of optically active allylic carbonates underwent complete alpha-to-gamma chirality transfer with anti-stereochemistry to produce optically active allylboronates having a boron-substituted stereogenic center. 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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gamma-Aryl-beta-ketoesters can be prepared in one step from aryl bromides and bis(trimethylsilyl) enol ethers using catalytic amounts of Pd(dba)2/t-Bu3P and stoichiometric amounts of Bu3SnF. The wide range of gamma-(hetero)aryl-beta-ketoesters that can be obtained illustrate the scope and limitations of this novel Hauser-Heck combination. gamma-Aryl-beta-ketoesters with a 1,3-dioxane acetal in the ortho position can easily be transformed into the hydroxy naphthoate in very good yield. Aqueous formic acid at 65 C provides optimal conditions for this deprotective aromatization.

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

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Palladium catalyzed Negishi, Suzuki and Stille cross-coupling reactions of enantiopure 2,2?-diiodo-1,1?-binaphthyl with the corresponding 1,1?-dimetalloferrocenes gave the C2-symmetric binaphthyl bridged ferrocene 1-1,1?-(1,1?-binaphthyl-2,2?-diyl)ferrocene (1). The latter was obtained by Stille coupling with the bis(trimethylstannyl) derivative but not with the bis(tributylstannyl) one. Products of alkyl group transfer from tin to binaphthyl were obtained as the main products in both cases. The stereochemical result of these cross-coupling reactions in the positions 2 and 2? of 1,1?-binaphthyl depends on the reactivity of 1,1?-dimetalloferrocenes. Negishi coupling proceeds stereoconservatively (affording enantiopure product 1). Complete racemization of binaphthyl moiety occurs during the reactions with less reactive boron and tin organometallics. Proposed different reaction pathways include C1-symmetric palladium(II) intermediate in the former and configurationally unstable C2-symmetric pallada(IV)cyclic intermediate in the latter cases. In contrast to the cross-coupling reactions, free radical arylation of ferrocene with enantiopure 1,1?-binaphthyl-2,2?-bisdiazonium salt gave predominantly oligomeric binaphthyl bridged ferrocenes and only traces of the partially racemized product 1.

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

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Treatment of alkynes with carbon monoxide and alcohols, using catalytic amounts of Pd(dba)2 or Pd(OAc)2 and 1,4-bis(diphenylphosphino)butane, affords unsaturated esters. The regiochemistry is opposite to that found using a formate ester instead of alcohol, and the process is applicable to tertiary esters.

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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 steroidal 1,4-diphosphines 3alpha- and 3beta-diphenylphosphino-2alpha-(2′-diphenylphosphinoethyl)-5alpha-cholestanes and their 5H-benzophosphindole derivatives have been prepared and shown to be useful ligands in asymmetric hydrogenation reactions.Interestingly the 3alpha- and 3beta-derivatives lead to opposing enantioselection preferences when used in these reactions.A steroidal 1,3-diphospine, 3alpha-diphenylphosphino-2alpha-diphenylphosphinomethyl-5alpha-cholestane, has been prepared as a mixture containing some of the 3beta-epimer.The 3alpha-1,3-diphosphine led to similar enantioselection in hydrogenation reactions as the 3alpha-1,4-diphosphine, and a model is proposed to explain the sense of the enantioselectivity in the 1,4- and 1,3-diphosphines.A steroidal 1,6-diphosphine has also been prepared but leads to lower optical yields in the hydrogenation reactions.These ligands have been shown to lead to only poor to moderate optical yields when used in asymmetric carbon-carbon bond forming reactions.

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

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We have developed a novel method for synthesizing trisubstituted cyclopropane derivatives by a palladium-catalyzed intramolecular allylic alkylation of alpha-aryl esters. By using alpha-aryl alpha-(methoxycarbonyl) gamma-vinyl gamma-lactones as substrates, decarboxylative formation of pi-allylpalladium(II) intermediates followed by an intramolecular allylic alkylation of the ester enolates proceeded in the presence of 5 mol% of a palladium catalyst, producing 1-aryl-1-(methoxycarbonyl)-2-vinylcyclopropanes in good to excellent yields and high diastereoselectivities. The relative configuration of the major isomer was determined by transforming the product into a known intermediate of milnacipran synthesis. When we extended our method to asymmetric catalysis, we obtained methyl (1S,2S)-1-phenyl-2-vinylcyclopropanecarboxylate in up to 55% ee by using (S)-[2?-(diphenylmethoxy)-1,1?-binaphthalen-2-yl](diphenyl)phosphine as a chiral monodentate phosphorus ligand.

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