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With hepta-1,6-diene and diallyl ether, Pd0 and Pt0 form highly reactive homoleptic dinuclear M2(1,6-diene)3 complexes, which are cleaved by donors L (e.g. C2H4, phosphanes, phosphites, isonitriles) to afford mononuclear derivatives L-M(1,6-diene); the X-ray structure of (Me3P)Pd{(eta2-CH2=CHCH2) 2O} has been determined.

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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 first Pd-catalyzed Mizoroki-Heck-type reaction of [Ph2SRfn][OTf] with alkenes is described. The reaction of [Ph2SRfn][OTf] (Rfn = CF3, CH2CF3) with alkenes in the presence of 10 mol% Pd[P(t-Bu)3]2 and TsOH at room temperature provided the corresponding phenylation products in good to high yields. The bases that benefit the traditional Mizoroki-Heck reactions severely inhibited the transformation with [Ph2SRfn][OTf], whereas acids significantly improved the reaction. This protocol supplies a new class of cross-coupling partners for Mizoroki-Heck-type reactions and gains important insights into the reactivity of phenylsulfonium salts either with or without fluorine-containing alkyl groups as the promising phenylation reagents in organic synthesis.

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

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(Chemical Equation Presented) Isolated truth: The synthesis, structures, and reductive elimination chemistry of arylpalladium(II) phenoxide and alkoxide complexes with a single bulky phosphine ligand are reported. These complexes are true intermediates in palladium-catalyzed etherification of aryl halides. They undergo reductive elimination of the alkyl aryl ether directly from the isolated complex (see scheme), and the rates of these reductive eliminations are slower than those from related arylpalladium amido complexes. Ad = adamantyl.

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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 compounds of Formula (I), and solvates, hydrates, and pharmaceutically acceptable salts thereof, wherein X1, X1′, X1″, R1, R2 and R3 are as defined herein, useful as FLAP modulators. The invention also relates to pharmaceutical compositions comprising compounds of Formula (I). Methods of making and using the compounds of Formula (I) are also within the scope 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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Construction of sterically congested all-carbon quaternary centers represents a formidable challenge in synthetic chemistry. The method described herein provides direct and facile access to a series of structurally diverse and synthetically useful aliphatic aldehydes, bearing an all-carbon alpha-vinyl quaternary center and a 1,5-diene functionality, through Pd-catalyzed umpolung of vinylethylene carbonates (VECs). The reaction features electrophilic-to-nucleophilic reactivity reversal of the VEC-derived pi-allyl-palladium intermediate via an unusual beta-hydride elimination process, and the resultant enolate is chemoselectively coupled with allylic acetate to form an alpha-vinyl aldehyde embedded with an all-carbon quaternary center.

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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 series of disilane-bridged donor-acceptor architectures 1-9 containing strong electron-donating and -withdrawing substituents were designed and synthesized in acceptable yields. The substituents substantially affected the fluorescence and nonlinear optical properties of the compounds. In the solid state, the compounds showed purple-blue fluorescence (lambdaem = 360-420 nm) with high quantum yields (up to 0.81). Compound 3, which had p-N,N-dimethylamino and o-cyano substituents, exhibited optical second harmonic generation (activity 2.9 times that of urea, calculated molecular hyperpolarizability beta = 1.6 × 10-30 esu) in the powder state. Density functional theory calculations for the ground and excited states indicated that both the locally excited state and the intramolecular charge transfer excited state make important contributions to the luminescence behavior.

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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 strategy for the synthesis of the lycopodium alkaloid dihydrolycolucine (1) has been investigated. Synthetic routes were developed based on N-acylpyridinium salt chemistry to prepare target fragments 3 and 4 that could ultimately converge to the natural product. Key reactions include IMDA cycloadditions and retro-Mannich ring-openings to form both the AB and the EF ring fragments. The ring C precursor was prepared using pyridine substitution and directed lithiation chemistry. A Suzuki cross-coupling of rings C and EF led to the CEF ring fragment. Initial attempts at closure of the seven-membered D ring were unsuccessful.

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

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Four three-coordinate arylpalladium amido complexes with a single hindered phosphine were isolated and structurally characterized. Each possessed a T-shaped geometry. Several of these complexes possessed true three-coordinate structures that lacked any additional coordination by ligand C-H bonds. All of the three-coordinate complexes underwent reductive elimination to form the corresponding triarylamine. A comparison of the rate of reaction of the three-coordinate compounds demonstrated that the rate of elimination from the pentaphenylferrocenyl di-tert-butylphosphine complex were the fastest. A comparison of the rates of reactions between three-coordinate and four-coordinate complexes showed that the rates were much faster from the three-coordinate complexes. 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 treatment of aryl iodides with tris(trimethylsilyl)silane in the presence of Pd(P(tBu)3)2 and the Huenig base leads to the formation of hypersilylated aromatic products in good to excellent yields without cleavage of weak Si-Si bonds under mild conditions. The Royal Society of Chemistry.

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

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Both symmetrical and unsymmetrical cyclophanes containing disilane units, tetrasila[2.2]cyclophanes 1-9, were synthesized. The syn and anti conformations and the kinetics of inversion between two anti-isomers were investigated by X-ray diffraction and variableerature NMR analysis, respectively. The flipping motion of two aromatic rings was affected by the bulkiness of the aromatic moiety (1 vs 6), the phase (solid vs solution), and the inclusion by host molecules (1 vs 1?[Ag2L]2+). The photophysical, electrochemical, and structural properties of the compounds were thoroughly investigated. Unsymmetrical tetrasila[2.2]cyclophanes 5-8 displayed blue-green emission arising from intramolecular charge transfer. Compound 6 emitted a brilliant green light in the solid state under 365 nm irradiation and showed a higher fluorescence quantum yield in the solid state (phi = 0.49) than in solution (phi = 0.05). We also obtained planar chiral tetrasila[2.2]cyclophane 9, which showed interesting chiroptical properties, such as a circularly polarized luminescence (CPL) with a dissymmetry factor of |glum| = ca. 2 × 10-3 at 500 nm. Moreover, an organic green light-emitting diode that showed a maximum external quantum efficiency (next) of ca. 0.4% was fabricated by doping 4,4?-bis(2,2?-diphenylvinyl)-1,1?-biphenyl with 6.

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