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Facile Synthesis of alpha-Keto Acids and Esters by Palladium-Catalyzed Decarboxylation Reactions of Diallyl alpha-Oxalcarboxylates

Reaction of diallyl alpha-oxalcarboxylates with formic acid in the presence of palladium catalyst gave alpha-keto acid in good yields.When the reaction was carried out without formic acid, decarboxylation-allylation took place to give allyl beta-allyl-alpha-keto carboxylates.

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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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Development and Analysis of a Pd(0)-Catalyzed Enantioselective 1,1-Diarylation of Acrylates Enabled by Chiral Anion Phase Transfer

Enantioselective 1,1-diarylation of terminal alkenes enabled by the combination of Pd catalysis with a chiral anion phase transfer (CAPT) strategy is reported herein. The reaction of substituted benzyl acrylates with aryldiazonium salts and arylboronic acids gave the corresponding 3,3-diarylpropanoates in moderate to good yields with high enantioselectivies (up to 98:2 er). Substituents on the benzyl acrylate and CAPT catalyst significantly affect the enantioselectivity, and multidimensional parametrization identified correlations suggesting structural origins for the high stereocontrol.

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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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Catalytic Enantioselective Synthesis of 2-Aryl Chromenes and Related Phosphoramidite Ligands and Catalyst Compounds

Methods to access 2-aryl chromene compounds via an asymmetric catalytic process.

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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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Reductive cyclization of halo-ketones to form 3-hydroxy-2-oxindoles via palladium catalyzed hydrogenation: a hydrogen-mediated Grignard addition

Abstract The reductive cyclization of N-oxoacyl ortho-bromoanilides to form 3-hydroxy-2-oxindoles under the conditions of palladium catalyzed hydrogenation is described. This work may be viewed as a prelude to intermolecular hydrogen-mediated Grignard-type reductive couplings of organic halides with carbonyl compounds.

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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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Reactions of palladium(0) olefin complexes stabilized by some different hetero- and homo-ditopic spectator ligands with propargyl halides

Several new allenyl and propargyl complexes have been obtained by oxidative addition with propargyl chlorides of palladium (0) olefin complexes stabilized by N?N, P?P, N?P, N?S. and N?C homo? and hetero?ditopic spectator ligands. The oxidative addition of some of the isolated palladium(0) olefin derivatives with 3?chloro?1?propyne and 3?chloro?1? phenyl?propyne has been investigated and the ensuing tautomeric mixtures bearing propargyl and allenyl fragmenst eta1? coordinated isolated. As a consequence of a detailed kinetic study, we have analyzed the influence of the electronic and steric parameters of the involved reactants and hypothesized the mechanism of reaction. The tautomeric rearrangement of one allenyl isomer into its propargyl counterpart was also investigated and in this case the complete determination of all the rate constants involved has been obtained. Beside these studies, two very rare eta3?propargyl palladium derivatives have been isolated and characterized.

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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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Enantioselective C2-Alkylation of Indoles through a Redox-Relay Heck Reaction of 2-Indole Triflates

A palladium-catalyzed enantioselective redox-relay Heck reaction of 2-indole triflates and disubstituted alkenes is reported. This process combines readily available indole triflates with a variety of alkenes to afford a range of indole derivatives bearing a stereocenter adjacent to C2. Enantioselectivity is achieved through use of a simple pyridine-oxazoline ligand. Tuning the electronics of the indole, through judicious choice of N-protecting group, is required to ensure selective beta-hydride elimination away from the indole core. Utility of this method is highlighted in a modular formal synthesis of an S1P1 agonist precursor developed by Merck.

We¡¯ll also look at important developments in the pharmaceutical industry because understanding organic chemistry is important in understanding health, medicine, the role of 52522-40-4, and how the biochemistry of the body works.category: catalyst-palladium

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

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The effect of diethylamine on Stille alkylations with tetraalkylstannanes

The addition of diethylamine to Stille alkylation reactions using stannanes improves yields by reducing beta-hydride elimination and reduction reactions, it also serves as a substitute for other additives such as Cu(I)I.

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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 enantioselective synthesis of carbanucleosides

A general strategy has been developed for enantioselective synthesis of diverse carbanucleosides. The key step is a Pd(0)-catalyzed enantioselective allylic amination of cis-3,5-dibenzoyloxycyclopent-2-ene 10a with the nucleobase. With guanine-derived nucleobase 13 and chiral ligand 9, a 93-96% ee was obtained, while 6-chloropurine and chiral ligand 8 gave 94% ee. The reaction was followed by a second Pd(0)-catalyzed allylic alkylation with phenylsulfonyl(nitro)methane 6. The nitrosulfone, thus obtained, served as a versatile intermediate for divergent synthesis in which the phenylsulfonyl(nitro)methyl group is a surrogate for the hydroxymethyl side chain. With the guanine-derived nucleobase 13, (-)-carbovir was obtained in only four steps from 10a. With 6-chloropurine as an adenine equivalent, the obtained nitrosulfone intermediate 26 could be converted into both (-)- aristeromycin and (-)-neplanocin A as well as their 2′,3′-diepi isomers.

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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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Preparation and Characterization of Palladium(I) and Platinum(I) Dinuclear Complexes Bridged by 2-(Dimethylphosphino)pyridine

A series of dinuclear complexes containing Me2Ppy (=2-(dimethylphosphino)pyridine) as a bridging ligand, (M, M’=Pd(I), Pt(I); X=Cl, Br, and I), have been prepared by reactions between and (dba=1,5-diphenyl-1,4-pentadien-3-one).In these reactions it has been found by 31P<1H>NMR studies that a dimeric head-to-head isomer was formed in the first place and then isomerized to a head-to-tail isomer.The reactions for analogous Ph2Ppy (=2-(diphenylphosphino)pyridine) complexes have been also examined in the same manner.The monomeric Pd(II) complexes reacted more rapidly than did the corresponding Pt(II) complexes in these dimerization and isomerization reactions.For each halogeno series of the Me2Ppy and Ph2Ppy complexes, it seems that the dimerization occurs faster in the order of ClBr>I.The Me2Ppy complexes isomerized to a head-to-tail isomer more rapidly than did the Ph2Ppy complexes, indicating a larger trans effect of Me2Ppy than Ph2Ppy.

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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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Access to Difluoromethylene-Skipped 1,4-Diynes with gem-Difluoropropargyl Bromide

Difluoromethylene (CF2)-skipped 1,4-diynes are a versatile synthon in organic synthesis, but efficient methods to access such a fluorinated structural motif are very limited. Herein, we report an efficient method for catalytic synthesis of CF2-skipped 1,4-diynes through palladium-catalyzed cross-coupling between terminal alkynes and gem-difluoropropargyl bromide. The reaction exhibits high functional group tolerance and broad substrate scope. Applications of the method led to a series of important difluorinated molecules that are of interest in medicinal chemistry.

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