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A palladium-catalyzed dearomative syn-1,4-oxyamination protocol using non-activated arenes has been developed. This one-pot procedure utilizes arenophile chemistry, and the corresponding para-cycloadducts are treated with oxygen nucleophiles via formal allylic substitution, providing direct access to syn-1,4-oxyaminated products. The reaction conditions permit a range of arenes, as well as different O-nucleophiles, such as oximes and benzyl alcohols. Moreover, this process was established in an asymmetric fashion, delivering products with high enantioselectivity. The dearomatized products are amenable to a multitude of further derivatizations ranging from olefin chemistry to C?H activation, giving rise to a diverse set of new functionalities. Overall, this dearomative functionalization offers rapid and controlled formation of molecular complexity, enabling straightforward access to functionalized small molecules from simple and readily available arenes.

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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 novel compounds which are inhibitors of CRAC channel activity. This invention also relates to pharmaceutical compositions containing them, process for their preparation and their use in therapy.

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

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This invention concerns heterocyclic derivatives of formula (I) which are useful in inhibiting oxido-squalene cyclase, processes for their preparation and pharmaceutical compositions containing them. The present invention is also concerned with heterocyclic derivatives capable of inhibiting cholesterol biosynthesis and hence the lowering cholesterol levels in blood plasma. The present invention also relates to methods of using such heterocyclic derivatives in diseases and medical conditions such as hypercholesterolemia and atherosclerosis.

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

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Three donor-acceptor polymers based on (3E,7E)-3,7-bis(2-oxoindolin-3-ylidene)benzo-[1,2-b:4,5-b]-difuran-2,6(3H,7H)-dione (BIBDF) and three kinds of dialkylated bithiophenes with head-to-head (HH), head-to-tail (HT), and tail-to-tail (TT) connectivity were synthesized by the Stille coupling reaction. Their photophysical and electrochemical properties, electronic device performance, and microstructure were investigated. We found that the alkyl chains substituted near the thiophene-thiophene connection cause less steric hindrance than those near the BIBDF-thiophene connection. Therefore PBIBDF-HH exhibited the preferred planarity, crystallinity, and molecular orientation, yielding the highest field-effect mobility. A maximum electron mobility of 1.23 cm2 V-1 s-1 and a maximum hole mobility of 0.37 cm2 V-1 s-1 were obtained for PBIBDF-HH-based devices. These results show that the substitution sites on the bithiophene units play an important role in the determination of molecular organization and the resulting device performance.

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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 microwave-assisted method has been developed for the synthesis of tri-substituted pyrazoles via direct N-heterocyclization of hydrazines with metal-acetylacetonate and -dibenzylideneacetonate without using any base or additives. Most importantly, the synthesis of 1-aryl-5-phenyl-3-styryl-1H-pyrazoles was achieved in a single step using hydrochloride salt of various phenylhydrazines and this is the first report for direct construction of these molecules. The reaction medium and microwave conditions play a critical role for their selective product formation during the reaction. The present reaction explored the usage of metal-diketonic complexes as reaction substrates providing acetylacetone and dibenzylideneacetone moieties to directly participate in cyclization with hydrazines to form the corresponding pyrazoles in excellent yields. The present protocol introduces the important N-heterocyclic moieties in the final structures, giving the reaction great applications from a medicinal chemistry perspective, particularly in the late stage modification strategies in drug discovery.

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

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Mild and sweet: The title reaction proceeds under mild conditions with high regio- and diastereoselectivity (see scheme, PG=protecting group, DiPPF=1,1?-bis(diisopropylphosphino)ferrocene). This reaction is suitable for a wide range of glycal-derived gamma-ketone esters and affords C-glycosides with exclusive beta-selectivity. The method was further applied to a concise formal synthesis of aspergillideA. 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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Recent development of donor?acceptor (D?A) structure copolymers has led to the remarkable enhancement of mobility over 10 cm2 (V s)?1 in organic semiconductors. Despite these achievements, a thorough understanding of the correlation between molecular structure and charge transport properties is still not achieved. With this goal in mind, the electrical properties of three copolymers based on the naphthalenediimide (NDI) acceptor with different donor units are compared, and the effect of increasing donor length on the electronic structure of semiconductors and the resulting charge transport performance is studied. Structural and morphological characterizations are done to reveal the macro transport properties of the semiconductor films. Then, electrical measurements of the field-effect transistors at variable temperatures are carried out to probe the charge transport property of the semiconductor films. Overall, it is found that the increasing of the donor length from one to three thiophene units would reduce the energetic disorder in the semiconductor films. Meanwhile, the electron cloud overlap between acceptor units would be weakened, which is detrimental to electron transport. Thus, a trading-off between energetic disorder and electron cloud overlap is critical for achieving high mobility in this NDI?based copolymer system.

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

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Perylene bisimide (PBI) unit has been widely used to design conjugated materials, which can be used as electron acceptor in organic solar cells due to its strong electron-deficient ability. In this work, a conjugated polymer based on PBI dimer as monomer was designed, synthesized, and compared to the conjugated polymer containing single PBI as repeating units. The two conjugated polymers were found to have similar molecular weight, absorption spectra and energy levels. Density functional theory calculation revealed that the PBI dimer-based polymer exhibited highly twisted conjugated backbone due to the large dihedral angle between the two PBI units. The PBI-based polymers as electron acceptor were applied into polymer-polymer solar cells, in which PBI dimer-based polymer solar cells were found to show a high short circuit current density (Jsc = 11.2 mA?cm?2 and a high power conversion efficiency (PCE) of 4.5%. In comparison, the solar cells based on PBI-based polymer acceptor only provided a Jsc of 7.2 mA?cm?2 and PCE of 2.5%. The significantly enhanced PCE in PBI dimer-based solar cells was attributed to the mixed phase in blended thin films, as revealed by atom force microscopy. This study demonstrates that PBI dimer can be used to design polymer acceptors for high performance polymerpolymer solar cells.

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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 general for­mula I, wherein the groups R1, R2 and m are defined as in claim 1, which have valuable pharmacological properties, in particu­lar bind to the GPR40 receptor and modulate its activity. The compounds are suitable for treatment and prevention of dis­eases which can be influenced by this receptor, such as meta­bolic diseases, in particular diabetes type 2.

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

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C – S coupling: A variety of arylthio-substituted heterocycles can be prepared through C – S coupling of the corresponding halide-substituted heterocycles by using a mixed-ligand palladium catalyst, [Pd2(dba) 3]/ Xantphos/CyPF-tBu (see scheme; dba=dibenzylideneacetone). This catalytic system is extremely powerful and efficient, allowing even C – Cl bond activation.

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