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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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A new method for the synthesis of polysubstituted conjugated dienes is described, through the palladium-catalyzed cross-coupling between N-tosylhydrazones and alkenyl bromides. The reaction proceeds efficiently when a combination of a highly substituted bromoalkene and a hydrazone derived from a ketone are employed, pointing to the convenience of a sterically encumbered environment. This unprecedented process allows for the stereocontrolled preparation of highly substituted dienes and polyenes. (Figure presented.).

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

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Chlorophyll and bacteriochlorophyll pigments are important porphyrinoids, which play key roles in light absorption, energy migration/transfer, and electron transfer in natural photosynthesis. Dyads of such pigments have attracted much attention from the viewpoints of mimicking photosynthetic light-harvesting and charge-separating systems. In this study, we report the synthesis and optical properties of heterodyads of zinc chlorin and free-base bacteriochlorin covalently linked by linear rigid substituents at the 20-position, which were prepared from naturally occurring chlorophyll-a. A free-base bacteriochlorin moiety accepted the singlet excitation energy from the zinc chlorin in the heterodyads. In the co-aggregate systems of heterodyads with chlorosomal self-assemblies, the latter transfers the singlet excitation energy to the bacteriochlorin moiety of the former, which are useful for artificial chlorosomal supramolecular light-harvesting systems.

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

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Here, we present an unprecedented formal [3 + 2] cycloaddition of para-quinone methides with vinyl epoxides/cyclopropanes to deliver a wide range of spiro[4.5]decanes in high efficiency and stereoselectivity. The commercial availability of the catalysts and reagents, together with the convenient procedure, makes it an attractive method in asymmetric synthesis.

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

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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Functionalized chiral carbazolones with alpha-quaternary carbon centers are formed through the ligand-controlled Pd-catalyzed enantioselective decarboxylative allylic alkylation of carbazolones (see scheme). This catalytic asymmetric reaction was employed as the key step in the total synthesis of aspidospermidine and (+)-kopsihainanineA. 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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The invention provides compounds of formulae (I) and (II) and pharmaceutical compositions thereof, which are useful as protein kinase inhibitors, as well as methods for using such compounds to treat, ameliorate or prevent a condition associated with abnormal or deregulated kinase activity. In some embodiments, the invention provides methods for using such compounds to treat, ameliorate or prevent diseases or disorders that involve abnormal activation of c-kit or c-kit and PDGFR (PDGFRcalpha PDGFRbeta) kinases

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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 stereospecific cross-coupling reaction of anomeric nucleophiles with diaryliodonium triflates resulting in the synthesis of aryl C-glycosides is reported. This process capitalizes on a stereoretentive reaction of configurationally stable C1 stannanes and is promoted by a palladium catalyst in the presence of a bulky phosphine ligand that suppresses the undesired beta-elimination. The utility of this reaction has been demonstrated in the preparation of a series of C-glycosides derived from common saccharides resulting in exclusive transfer of anomeric configuration from the anomeric nucleophile to the product, and in the synthesis of empagliflozin, a commercial antidiabetic drug.

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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 stability of five different [Pdn(N-donor)m]2n+ assemblies was examined by performing disassembly experiments with pyridine and with trifluoroacetic acid. Pyridine-induced disassembly was found to be most pronounced for Pd complexes containing N-donor ligands of low basicity. At the same time, these assemblies displayed high acid resistance. The contrasting stability in the presence of acid or pyridine can be used for the pH-controlled switching between different metallosupramolecular structures.

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

Awesome Chemistry Experiments For Bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II)

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A novel methodology for the synthesis of highly substituted pyridines based on the palladium-catalyzed enolate alpha-alkenylation of ketones is presented; the formation of aromatic compounds is a new direction for this catalytic C-C bond forming reaction. In the key step, a protected beta-haloalkenylaldehyde participates in alpha-alkenylation with a ketone to afford a 1,5-dicarbonyl surrogate, which then undergoes cyclization/double elimination to the corresponding pyridine product, all in one pot. The beta-haloalkenylaldehyde starting materials can be obtained from the corresponding methylene ketone via Vilsmeier haloformylation. Using this concise route, a variety of highly substituted pyridines were synthesized in three steps from commercially available compounds. (Chemical Equation Presented).

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