Awesome Chemistry Experiments For 1,1′-Bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex

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(Chemical Equation Presented) We describe a concise synthesis of the structurally novel fungal extremophile metabolite berkelic acid, an effort leading to an unambiguous assignment of C22 stereochemistry. Our synthetic approach was inspired by the recognition that berkelic acid displays structural characteristics reminiscent of two other fungal metabolites, spicifernin and pulvilloric acid. Based on this notion, we executed a synthesis that features a Ag-catalyzed cascade dearomatization-cycloisomerization-cycloaddition sequence to couple two natural product inspired fragments. Notably, a spicifernin-like synthon was prepared with defined C22 stereochemistry in seven steps and three purifications (24-28% overall yield). A potentially useful anti-selective conjugate propargylation reaction was developed to introduce the vicinal stereodiad. An enantioconvergent synthesis of the other coupling partner, the aromatic precursor to pulvilloric acid methyl ester, was achieved in eight steps and 48% overall yield. The total synthesis of berkelic acid and its C22 epimer was thus completed in a 10 step linear sequence and 11-27% overall yield.

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

A new application about 1,1′-Bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex

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A new heterometallic dyad composed of a zinc porphyrin linked by bisethynyl quaterthiophene to a gold porphyrin was synthesized according to a stepwise modular approach. The latter dyad and the parent reference compounds (porphyrin-ethynylquaterthiophene) were characterized by electrochemistry, spectroelectrochemistry, and femtosecond transient absorption spectrocopy. We showed that light excitation of the zinc or the gold porphyrin induces a very fast and quantitative charge separation over a distance of 25 A which occurs through a superexchange mechanism. The lifetime of the charge-separated state is 3.3 ns in toluene and 100 ps in dichloromethane, and it recombines to the ground state in both solvents.

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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 relates to a compound represented by formula (I) and pharmaceutically acceptable salts thereof are disclosed as useful for treating or preventing diabetes, hyperlipidemia, obesity, NASH, inflammation related disorders, and related diseases and conditions. The compounds are useful as agonists of the G-protein coupled receptor GPR120. Pharmaceutical compositions and methods of treatment are also included.

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

The important role of 1,1′-Bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex

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Trifluoroethylation: Aryl boronic acids can be catalytically trifluoroethylated with the readily available reagent CF3CH 2I (see scheme, dba=dibenzylideneacetone). The reaction tolerates a variety of functional groups and can be extended to the trifluoroethylation of aryl or alkenyl boronic esters. The method is also suitable for the late-stage installation of the CF3CH2 group into target molecules. Copyright

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

The Absolute Best Science Experiment for Pd2(DBA)3

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A straightforward synthesis of cyclopropenylidene-stabilized phosphenium cations 1 a-g through the reaction of [(iPr2N)2C 3+Cl]BF4 with secondary phosphines is described. Their donor ability was evaluated by analysis of the CO stretching frequency in Rh complexes [RhCl(CO)L2](BF4)2 and electrochemical methods. The cyclopropenium ring induces a phosphite-type behavior that can be tuned by the other two substituents attached to the phosphorus atom. Despite of the positive charge that they bear, phosphenium cations 1 a-g still act as two-electron donor ligands, forming adducts with PdII and PtII precursors. Conversely, in the presence of Pd0 species, an oxidative insertion of the Pd atom into the C carbene-phosphorus bond takes place, providing dimeric structures in which each Pd atom is bonded to a cyclopropenyl carbene whi Copyright

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

Extracurricular laboratory:new discovery of 1,1′-Bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex

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Disubstituted pyridine/pyrimidine ferrocenyl complexes have been obtained by mechanically induced Sukuzi coupling reactions in the solid state. It is shown that the solventless process is much faster, and more selective, than the same reaction carried out in solution. The synthesis and structure of the complex [Fe(eta5-C5H4-4-C5H 4N)(eta5-C5H4-3-C 4H3N2)] are reported as a test case.

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

Extended knowledge of 1,1′-Bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex

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Sterically hindered 2,5-diphenyl-and 2,3,5-triphenyl-1-vinylpyrroles have been obtained by the vinylation of the corresponding NH-pyrroles with acetylene in superbasic catalytic system KOH-DMSO in up to 78% yield. 2,3,5-Triphenyl-1- vinylpyrrole has also been obtained in 75% yield by the regioselective bromination of 2,3-diphenyl-1-vinylpyrrole with subsequent cross-coupling of 5-bromo-2,3-diphenyl-1-vinylpyrrole with phenylmagnesium bromide in the presence of dichloro[1,1?-bis(diphenylphosphino)ferrocene]palladium(II). 2,5-Diphenyl- and 2,3,5-triphenyl-1-vinylpyrroles undergo a free-radical polymerization (AIBN, 80 C) to form oligomers in 11 and 27% yield, respectively.

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

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Previous enantioselective Pd0-catalyzed C?H activation reactions proceeding via the concerted metalation-deprotonation mechanism employed either a chiral ancillary ligand, a chiral base, or a bimolecular mixture thereof. This study describes the development of new chiral bifunctional ligands based on a binaphthyl scaffold which incorporates both a phosphine and a carboxylic acid moiety. The optimal ligand provided high yields and enantioselectivities for a desymmetrizing C(sp2)?H arylation leading to 5,6-dihydrophenanthridines, whereas the corresponding monofunctional ligands showed low enantioselectivities. The bifunctional system proved applicable to a range of substituted dihydrophenanthridines, and allowed the parallel kinetic resolution of racemic substrates.

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

Discovery of Pd2(DBA)3

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The design, synthesis, characterization, and application of a novel series of copolymers based on the electron deficient thieno[3,4-c]pyrrole-4,6-dione building block, copolymerized with either thieno[3,2-b]thiophene (PTPDTT) or thiophene (PTPDT), are reported. High molecular weights were obtained for PTPDTT via Stille polycondensation. For the PTPDTs, different molecular weights were achieved by varying the polymerization conditions. The increase in molecular weight (PTPDT-2) favors face-on alignment and increases the charge carrier mobility. Grazing-incidence wide-angle X-ray scattering measurements reveal higher crystallinity for PTPDTT with up to 5 orders of lamellar stacking compared to PTPDTs. All polymers show ambipolar charge transport with highly balanced hole and electron mobilities in organic field effect transistors (OFETs), which improve considerably upon thermal annealing. A shift of comonomer from simple thiophene in PTPDT-2 to planar and electron-dense thienothiophene in PTPDTT drastically changes the alignment from face-on to edge-on fashion. Consequently, the charge carrier mobility increases considerably by 1 order of magnitude in PTPDTT, reaching excellent charge carrier mobilities for both holes (0.11 cm2 V-1 s-1) and electrons (0.17 cm2 V-1 s-1). PTPDTT was tested as a donor material in combination with PC71BM as well as an acceptor material along with a donor polymer. As a donor material, a power conversion efficiency of 4.3% was reached in combination with PC71BM.

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

The Absolute Best Science Experiment for Bis(dibenzylideneacetone)palladium

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Iodo(aryl)palladium complexes, [PdI{C6H3 (CF3)2-3,5}(N-N)] (N-N = tmeda, bpy, 4,4?-dimethyl-2,2?-bipyridine (Me2bpy)), react with AgBF4 in CH3CN, acetone, and THF to yield stable cationic arylpalladium complexes [Pd{C6H3 (CF3)2-3,5}(N-N)(solv)]BF4. A similar reaction of AgBF4 with [PdI(C6H3Me2-3,5) (bpy)] in CH3CN gives [Pd(C6H3Me2- 3,5)(bpy)(CH3CN)]BF4. The complex does not change its NMR spectrum for 1 h at room temperature in CD3CN but undergoes decomposition upon dissolution in acetone to release 3,3?,5,5?- tetramethylbiphenyl. Addition of AgBF4 to acetone or THF solutions of [PdI(Ar)(bpy)] (Ar = Ph, C6H3Me2-3,5) and of [PdI(Ar)(Me2bpy)] (Ar = C6H4OMe-4, C6H3Me2-3,5) does not lead to isolation of the cationic arylpalladium complexes and causes intermolecular coupling of the aryl ligands to yield the corresponding biaryls. The reaction of AgBF4 with [PdI(C6H3Me2-3,5)(bpy)] in the presence of an excess amount of dimethyl acetylenedicarboxylate (DMAD) in CH3CN gives [Pd(CZ=CZ-CZ=CZ-C6H3Me2-3,5)(bpy) (CH3CN)]BF4 (Z = COOMe) via insertion of two acetylene molecules into the Pd-aryl bond. A similar reaction in acetone or THF causes insertion of three DMAD molecules into the Pd-aryl bond and cyclization of the formed Pd-(CZ=CZ)3-Ar group to give the product containing a cyclopentadiene structure in the ligand. [PdI(CZ=CZ-C6H3 Me2-3,5)(bpy)] reacts with AgBF4 in CH3CN to form a cationic complex, [Pd(CZ=CZ-C6H3Me2-3,5) (bpy)(CH3CN)]BF4. A series of cationic Pd complexes, formed through insertion of one, two, and three alkyne molecules into the Pd-aryl bond, are characterized by X-ray crystallography or NMR spectroscopy. Phenylallene reacts with [PdI(C6H3Me2-3,5) (bpy)] in the presence of AgBF4 to give [Pd{eta3-CH2C-(C6H3 Me2-3,5)CHPh}(bpy)]BF4 via insertion of the C=C double bond of the allene into the Pd-C bond of the cationic arylpalladium complex. The pi-allylpalladium complex crystallizes exclusively in a form with a syn-oriented phenyl substituent but exists in solution as a mixture of the isomers with a syn or anti phenyl substituent.

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