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Ring a ding: The meroterpenoid natural product (+)-liphagal has been synthesized enantioselectively in 19 steps from commercially available materials. The trans-homodecalin system was achieved by ring expansion followed by stereoselective hydrogenation. 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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Tetrameric and octameric 2,6-pyridylene ethynylene oligomers linked to a beta-D-glucopyranoside template through an o-phenylene linker were prepared and studied for their higher-order structure. These oligomers formed chiral helical structures through intramolecular hydrogen bonding between the ethynylpyridine moiety and the glucoside template. The rigidity of the o-phenylene linker stabilizes the helical structure to improve its CD activity and resistance against protic surroundings. Furthermore, the helical stabilization was enhanced by the addition of Cu(OTf)2 and Zn(NO 3)2 salts. Tetrameric and octameric 2,6-pyridylene ethynylene oligomers joined to a beta-D-glucopyranoside by a o-phenylene linker were prepared and their higher-order structure studied. The chiral helical structures formed by intramolecular H-bonding and linker stabilization improve CD activity and resistance to protic surroundings. Stabilization was enhanced with the addition of Cu(OTf)2 and Zn(NO3) 2 salts. 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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A palladium-catalyzed insertion copolymerization of vinyl chloride (VC) and ethylene gave chlorinated polyethylene with CH3CHCl(CH 2)n units (see scheme; C blue, O red, Pd orange, S yellow). The CH3CHCl end groups form by 2,1-insertion of VC into palladium hydride complexes, as revealed by detailed labeling studies. This first example of VC incorporation (up to 0.4 mol %) clearly shows that insertion (co)polymerization of VC is in principle feasible.

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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 provides common ligand mimics that act as common ligands for a receptor family. The present invention also provides bi-ligands containing these common ligand mimics. Bi-ligands of the invention provide enhanced affinity and/or selectivity of ligand binding to a receptor or receptor family through the synergistic action of the common ligand mimic and specificity ligand which compose the bi-ligand. The present invention also provides combinatorial libraries containing the common ligand mimics and bi-ligands of the invention. Further, the present invention provides methods for manufacturing the common ligand mimics and bi-ligands of the invention and methods for assaying the combinatorial libraries 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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UV irradiation of Pd(PtBu3)2 in n-hexane or THF gives the diamagnetic dinuclear complex 2, 2-methylpropene, and hydrogen.The complex was also obtained from the reaction of Pd(eta5-C5H5)(eta3-C3H5) with PtBu2H in toluene.Its crystal and molecular structure were determined by an X-ray diffraction study.Each Pd bears a terminal PtBu2H ligand and the two metal centers are bridged by two phosphido ligands.

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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 sodium salts of allyldimethylsilanol and 2-butenyldimethylsilanol undergo palladium-catalyzed cross-coupling with a wide variety of aryl bromides to afford allylated and crotylated arenes. The coupling of both silanolates required extensive optimization to deliver the expected products in high yields. The reaction of the allyldimethylsilanolate takes place at 85C in 1,2-dimethoxyethane with allylpalladium chloride dimer (2.5 mol %) to afford 73-95% yields of the allylation products. Both electron-rich and sterically hindered bromides reacted smoothly, whereas electron-poor bromides cross-coupled in poor yield because of a secondary isomerization to the 1-propenyl isomer (and subsequent polymerization). The 2-butenyldimethylsilanolate (E/Z, 80:20) required additional optimization to maximize the formation of the branched (gamma-substitution) product. A remarkable influence of added alkenes (dibenzylideneacetone and norbornadiene) led to good selectivities for electron-rich and electron-poor bromides in 40-83% yields. However, bromides containing coordinating groups (particularly in the ortho position) gave lower, and in one case even reversed, selectivity. Configurationally homogeneous (E)-silanolates gave slightly higher gamma-selectivity than the pure (Z)-silanolates. A unified mechanistic picture involving initial gamma-transmetalation followed by direct reductive elimination or sigma-pi isomerization can rationalize all of the observed trends.

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

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Some norbenzomorphans exhibit high affinity for sigma 1 and sigma 2 receptors, and varying the position of substituents on the aromatic ring of this scaffold has a significant effect on subtype selectivity. In particular, compounds bearing several different substituents at C7 of the norbenzomorphan ring system exhibit a general preference for the sigma 1 receptor, whereas the corresponding C8-substituted analogues preferentially bind at the sigma 2 receptor. These findings suggest that the norbenzomorphan scaffold may be a unique chemical template that can be easily tuned to prepare small molecules for use as tool compounds to study the specific biological effects arising from preferential binding at either sigma receptor subtype. In the absence of structural characterization data for the sigma 2 receptor, such compounds will be useful toward refining the pharmacophore model of its binding site.

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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 object of the present patent application are agents for the oxidative coloring of keratin fibers, particularly hair, based on a developer substance-coupler substance combination, characterized in that they contain at least one meta-aminophenol derivative of general formula (I), wherein R1 denotes hydrogen, a C1-C6 alkyl group, a C2-C4 hydroxyalkyl group, a C2-C4 dihydroxyalkyl group, a C1-C4 alkoxy group or a halogen atom; and R2 denotes hydrogen, a hydroxy group, a carboxylic group, an aminocarbonyl group or a hydroxymethyl group.

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

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Iterative growth of thiophene oligomers by single-step extensions has been realized by regioselective metalation of 3-substituted thiophenes with the Knochel-Hauser base (TMPMgCl·LiCl) and coupling with bromothiophene using a nickel catalyst. Treatment of 3-hexylthiophene with TMPMgCl·LiCl induces metalation at the 5-position selectively. Subsequent addition of 2-bromo-3-hexylthiophene and a nickel catalyst leads to the corresponding bithiophene. The obtained bithiophene is converted to the terthiophene and then to the quaterthiophene by repeating the similar protocol. A concise synthesis of MK-1 and MK-2, which are organic dye molecules bearing an oligothiophene moiety that are used in photovoltaic cells, has been achieved.

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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 catalysis derived from the dinuclear Pd(I)-Pd(I) complex, {[PtBu 3]PdBr}2, has been studied with experimental, computational, and spectroscopic techniques. Experimental selectivity studies were performed, and the reactivity was subsequently investigated with density functional theory (B3LYP-D and M06L) to deduce information on the likely active catalytic species. The reactivity with aryl chlorides and bromides was found to be inconsistent with direct catalytic involvement of the Pd(I) dimer but consistent with mononuclear Pd(0) catalysis. Computational studies suggest that precatalyst transformation to the active catalytic species does not proceed via a direct disproportionation mechanism; a reductive pathway is the most likely scenario instead. Through 31P NMR investigations it was identified that the combination of ArB(OH)2, KF, and water triggers the conversion of the precatalyst to Pd(PtBu3)2 and, most likely, Pd-black as a competing side process, explaining the incomplete conversions of aryl chlorides in Suzuki cross-coupling reactions under Pd(I) dimer conditions. New applications in highly regio- and chemoselective transformations in short reaction times at room temperature are also demonstrated.

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