Archives for Chemistry Experiments of Tris(dibenzylideneacetone)dipalladium-chloroform

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(Chemical Equation Presented) Split and run: A study of the asymmetric hydrogenolysis of an aryl-carbon-bromine bond in a naphthalene chromiumtricarbonyl complex shows the use of a new bulky phosphoramidite ligand to yield the product in highly enantiomerically enriched form (see scheme).

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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 mere presence or absence of PPh3 suffices to control the reactivity of bis(eta3-allyl)palladium complexes. In the absence of PPh3 they undergo chemoselective allylic addition to aldehydes or imines, even in the presence of allylic chlorides, whereas in the presence of PPh3 the Stille coupling reaction takes place chemoselectively, even when aldehydes or imines are also present (see scheme).

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

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Diastereo- and enantioselective cycloaddition of 3-nitroindoles with vinyl aziridine was realized under Pd-catalysis using commercially available Walphos as the ligand, affording pyrroloindolines in high yields with high diastereo- and enantioselectivities. The reaction can be scaled up to a gram scale and the reaction products are easily converted to amino pyrroloindoline and other pyrroloindoline derivatives.

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

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Ortho-palladated complexes of (Z)-2-aryl-4-arylidene-5(4H)-oxazolones have been prepared through oxidative addition. The reaction of (Z)-2-phenyl-4-(2- bromobenzylidene)-5(4H)-oxazolone (4) with Pd2(dba)3 · CHCl3 gives the six-membered cyclopalladated dinuclear complex [Pd(mu-Br)(o-C6H4CH=CNC(O)OCPh)]2 (7). The reaction of 7 with PPh3 gives dinuclear 9, which incorporates one phosphine per Pd atom through cleavage of the Pd-N bond, and preserves the bromide bridging system. However, reaction with PPh2Me gives mononuclear 8, which incorporates two phosphines as a results of the cleavage of the mu-Br system and N displacement. In contrast, the reaction of 7 with pyridine gives complex 12 due to simple cleavage of the Br bridge, leaving the N-bonding intact. Therefore, three different reaction pathways have been characterized. The reactivity of the Pd-C bond in 7 has also been examined, and functionalized oxazolones can be obtained. The reaction of 7 with PhI(OAc)2 in acetic acid gives the starting oxazolone C 6H4-2-Br-CH=CNC(O)OCPh (4), through the presumed oxidation of the Pd center and C-Br bond formation by reductive coupling. In contrast, the reaction of the acetate dlmer 14 with PhI(OAc)2 in acetic acid gives C 6H4-2-OAcCH=CNC(O)OCPh (20) through C-O coupling. When treatment of 7 with PhI(OAc)2 is performed in MeOH or EtOH, the oxazolones C6H4-2-OR-CH=CNC(O)OCPh (R = Me (18), Et (19)) are obtained. The reaction of 7 with CO in alcohols ROH gives cleanly the oxazolones C6H4-2-CO2RCH=CNC(O)OCPh (R = Me (21), iPr (22)) through CO migratory insertion into the Pd-C bond and further nucleophilic attack of the RO-fragment.

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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 studied the oxidative addition of some organic halides on palladium(0) dimethylfumarate complexes bearing heteroditopic (N-P or N-S) quinoline-based spectator ligands from the experimental and theoretical point of view. We have measured the half-life of some oxidative addition reactions carried out in two different solvents (CD2Cl2 and CD3CN). The reactions were studied under mild conditions by NMR and the reactivities of different oxidants towards the complexes under study were compared. The rates of reaction were influenced by the nature of the spectator ligands and the solvent. The thioquinoline derivatives display a higher reactivity than that of the phosphoquinoline complexes and in general the reaction rates are higher in CD3CN than in CD2Cl2, although such a behavior is not always observed. We propose a plausible mechanism for the oxidative reaction in different solvents based on the experimental results and an adequate computational approach. Finally, the solid state structures of two reaction products were resolved and reported.

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

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Participation of chiral sulfinyl functionality in palladium-catalyzed asymmetric reactions is demonstrated by using chiral sulfoxides as chiral ligands or chiral substrates. New chiral ligands, o-(phosphinoamino)phenyl and o-phosphinophenyl sulfoxides, have been developed. The structure of an intermediary palladium complex was determined by X-ray crystallographic analysis. The palladium-catalyzed asymmetric 1,3-rearrangements of (1,3-butadienyl)cyclopropanes bearing chiral sulfinyl groups to cyclopentenes are described. The participation of the chiral sulfinyl group to the palladium catalyst is described. (C) 2000 Elsevier Science Ltd All rights reserved.

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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 this communication, we report a palladium-catalyzed decarboxylative allenylation of benzyl carbonates and tert-butyl carbonates of 2,3-allenols with 3-oxocarboxylic acids. The reaction provides a new and straightforward approach to 3,4-dienyl ketones under mild conditions.

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

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Complementary methods for the transition-metal-catalyzed enyne cycloisomerizations of cyclic olefins have been developed. By using distinct ruthenium and palladium catalysts, decalins and 7,6-bicycles can be obtained with dichotomous stereochemical outcomes. The change in mechanism that accompanies the change in metal affords trans-fused 1,4-dienes with ruthenium and their cis-fused diastereomers under palladium catalysis. In the reactions under ruthenium catalysis, a coordinating group is required and acts to direct the metal to the same side of the carbocycle, resulting in the observed trans diastereoselectivity. Subtle changes in the carbocyclic substrate led to the discovery of a heretofore-unobserved mechanistic pathway, providing bicyclic cycloisomerization products under palladium catalysis and tricyclic products under ruthenium catalysis in N,N-dimethylacetamide (DMA). The differential effect of DMA supports a mechanism in which the coordination requirements of the two paths differ, allowing for the reaction to be shuttled through the metallacycle pathway (generating tricyclic products) when DMA is used as a solvent.

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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 new chiral auxiliary (R)-2-ethylthio-1-(phenylethyl)-(R)-binaphthyl phosphite, 1, and three stable Pd(0) olefin complexes containing this chelate, 2-4, have been synthesized. The structure of the maleic anhydride complex 3 has been determined by X-ray diffraction methods. Solution details for 2-4 and aspects of their dynamics have been elucidated via 2-D NMR spectroscopy. The fumaronitrile complex 2 exchanges intramolecularly, whereas the maleic anhydride and pentenedione derivatives, 3 and 4, respectively, exchange intermolecularly. Ligand 1 has been used as auxiliary in the Pd, Rh, and Ir regio- and enantioselective allylic alkylation reactions of PhCH=CHCH(OAc)R, R = H, Me, Et, with the anion of dimethyl malonate. Modest to good selectivities are reported.

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

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Binuclear complex of platinum (I) and palladium (I) showed superior activity in Suzuki-Miyaura coupling reaction of aryl halides with arylboronic acids compared to the sole palladium or platinum species. The catalyst showed good tolerance in water and coupling reactions were performed in water as a green solvent. Aryl iodides were reacted at room temperature and the reactions of aryl bromides were performed at 60 C.

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