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Palladium-catalyzed direct arylation of 5-halouracils and 5-halouracil nucleosides with arenes and heteroarenes promoted by TBAF

The 1-N-benzyl-5-iodo(or bromo)uracil undergoes Pd-catalyzed [Pd 2(dba)3] direct arylation with benzene and other simple arenes in the presence of TBAF in DMF without the necessity of adding any ligands or additives to give 5-arylated uracil analogues. The TBAF-promoted coupling also occurs efficiently with electron rich heteroarenes at 100 C (1 h) even with only small excess of heteroarenes. The protocol avoids usage of the arylboronic acid or stannane precursors for the synthesis of 5-(2-furyl, or 2-thienyl, or 2-pyrrolyl)uracil nucleosides, which are used as important RNA and DNA fluorescent probes. The fact that 1-N-benzyl-3-N-methyl-5-iodouracil did not undergo the TBAF-promoted couplings with arenes or heteroarenes suggests that the C4-alkoxide (enol form of uracil) facilitates coupling by participation in the intramolecular processes of hydrogen abstraction from arenes. TBAF-promoted arylation was extended into the other enolizable heterocyclic systems such as 3-bromo-2-pyridone. The pi-excessive heteroarenes also coupled with 5-halouracils in the presence of Pd(OAc)2/Cs2CO 3/PivOH combination in DMF (100 C, 2 h) to yield 5-arylated uracils.

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

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Enantioselective Synthesis of Homoallylic Azides and Nitriles via Palladium-Catalyzed Decarboxylative Allylation

Azides and nitriles are important building blocks for the synthesis of nitrogen-containing bioactive compounds. The first example of enantioselective palladium-catalyzed decarboxylative allylation of alpha-azido and cyano beta-ketoesters is reported. Indanone derivatives were obtained in 50-88% yield/77-97% ee and 46-98% yield/78-93% ee for azide and nitrile substituents, respectively. The required starting materials were synthesized in one step from ketoesters via electrophilic azidation and cyanation using benziodoxole hypervalent iodine reagents. The products could be easily converted into useful nitrogen-containing building blocks, such as triazoles, amides, or alpha- and beta- amino ketones.

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

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Catalyzed catalysis using carbophilic Lewis acidic gold and Lewis basic palladium: Synthesis of substituted butenolides and isocoumarins

(Figure Presented) A new strategy for gold and palladium dual-catalytic reactivity and turnover, called catalyzed catalysis, enhanced the synthetic usefulness of vinylgold intermediates by providing dual-catalytic carbon-carbon cross-coupling as an alternative to protodemetalation. This protocol enabled the synthesis of substituted butenolides and isocoumarins from allyl esters. Kinetic and spectroscopic experiments support a mechanism in which the Lewis acidic gold complex catalyzes both an initial rearrangement step and a subsequent Lewis basic palladium oxidative-addition step.

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

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Effect of methyl substitution on the diketopyrrolopyrrole-based semiconducting polymers for organic thin film transistors

Two semiconducting polymers, poly[2,5-bis(5-octylpentadecyl)-3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione-selenophene] (PDPP-Se) and poly[3,6-bis(4-methylthiophen-2-yl)-2,5-bis(5-octylpentadecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione-selenophene] (PMDPP-Se) were designed and synthesized. These polymers contain diketopyrrolopyrrole (DPP) and methyl-substituted DPP (MDPP) units as the acceptor building blocks, and selenophene as a counter donor unit. The introduction of methyl groups on the thiophene units flanked by the DPP core substantially affected its optical, electrochemical, and charge-transporting properties. Experimental results revealed that the introduction of electron-donating methyl groups raised the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of PMDPP-Se. Interestingly, the PMDPP-Se showed better co-planarity with the adjacent aromatic groups compared to PDPP-Se. Furthermore, the methyl-substituted polymer showed a transition behavior in its thin film morphology and crystal orientation with an increase in the annealing temperature, which induced an M-shape dependence of the field-effect mobility on the annealing temperature. PMDPP-Se recorded a maximum hole mobility muh = 1.31 cm2 V?1 s?1 at optimum phase, which is higher than that of PDPP-Se (muh = 0.86 cm2 V?1 s?1).

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

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Access to polysubstituted indoles or benzothiophenes via palladium-catalyzed cross-coupling of furfural tosylhydrazones with 2-iodoanilines or 2-iodothiophenols

Palladium-catalyzed cross-coupling of furfural tosylhydrazones with 2-iodoanilines or 2-iodothiophenols produces polysubstituted indoles or benzothiophenes, respectively. The reaction proceeds through 2-furylmethylene palladium iodide intermediates, which undergo furan ring opening followed by ring closure to form indoles or benzothiophenes. This reaction will expand the synthetic applications of furfural derivatives.

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

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Bi-diketopyrrolopyrrole (Bi-DPP) as a novel electron accepting compound in low band gap pi-conjugated donor-acceptor copolymers/oligomers

The synthesis and characterization of a novel 2,5-diketopyrrolo[3,4-c]pyrrole(DPP)-based accepting building block with the scheme DPP-neutral small linker-DPP (Bi-DPP) is presented, which was utilized as electron accepting moiety for low band gap pi-conjugated donor-acceptor copolymers as well as for a donor-acceptor small molecule. The electron accepting moiety Bi-DPP was prepared via a novel synthetic pathway by building up two DPP moieties step by step simultaneously starting from a neutral phenyl core unit. Characterization of the synthesized oligomeric and polymeric materials via cyclic voltammetry afford LUMO energy levels from -3.49 to -3.59 eV as well as HOMO energy levels from -5.07 to -5.34 eV resulting in low energy band gaps from 1.52 to 1.81 eV. Spin coating of the prepared donor-acceptor oligomers/polymers resulted in well-defined films. Moreover, UV-vis measurements of the investigated donor-acceptor systems showed a broad absorption over the whole visible region. It is demonstrated that Bi-DPP as an electron accepting moiety in donor-acceptor systems offer potential properties for organic solar cell devices.

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

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Highly Efficient Indoor Organic Solar Cells by Voltage Loss Minimization through Fine-Tuning of Polymer Structures

Herein, we report a detailed study on the optoelectronic properties, photovoltaic performance, structural conformation, morphology variation, charge carrier mobility, and recombination dynamics in bulk heterojunction solar cells comprising a series of donor-acceptor conjugated polymers as electron donors based on benzodithiophene (BDT) and 5,8-bis(5-bromothiophen-2-yl)-6,7-difluoro-2,3-bis(3-(octyloxy)phenyl)quinoxaline as a function of the BDT’s thienyl substitution (alkyl (WF3), alkylthio (WF3S), and fluoro (WF3F)). The synergistic positive effects of the fluorine substituents on the minimization of the bimolecular recombination losses, the reduction of the series resistances (RS), the increment of the shunt resistances (RSh), the suppression of the trap-assisted recombination losses, the balanced charge transport, the finer nanoscale morphology, and the deeper highest occupied molecular orbital (EHOMO) are manifested versus the alkyl and alkylthio substituents. According to these findings, the WF3F:[6,6]-phenyl-C71-butyric acid methyl ester (PC71BM)-based organic photovoltaic device is a rare example that features a high power conversion efficiency (PCE) of 17.34% under 500 lx indoor light-emitting diode light source with a high open-circuit voltage (VOC) of 0.69 V, due to the suppression of the voltage losses, and a PCE of 9.44% at 1 sun (100 mW/cm2) conditions, simultaneously.

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

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USE OF SUBSTITUTED 2 PHENYLBENZIMIDAZOLES AS MEDICAMENTS

The present invention relates to the use of a substituted 2-phenylbenzimidazole of formula I wherein R1, R2, R3, R 4, R5 and m have the meanings given in the claims, for the preparation of a medicament for the treatment or prevention of diseases involving glucagon receptors, as well as new compounds of formula I wherein R1 is a group of formula

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

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Luminescence properties of carborane-containing distyrylaromatic systems

A set of distyrylbenzene, distyrylbiphenyl and distyrylanthracene end-substituted with carborane clusters is introduced herein. All these compounds have been prepared from the corresponding styrene-containing carborane derivatives via Heck coupling reaction. High regioselectivity has been achieved yielding exclusively E isomers. All compounds have been fully characterized and the crystal structure of the distyrylbiphenyl end-substituted with Methyl-o-carborane was analyzed by X-ray diffraction. The absorption properties of compounds were elucidated by TD-DFT calculations, highlighting the importance of the aromatic core and pi-conjugation. It is worth noting that the luminescence properties of these systems depend on the aromatic core; in solution, benzene and biphenyl derivatives showed higher fluorescence emission than the anthracene ones and the presence of the carborane clusters does not induce any major change in fluorescence as compared to the pristine non-carborane containing partners. Nevertheless, all compounds exhibited low fluorescence quantum yields in aggregation state, which gives clear evidence of considerable intermolecular interactions between aggregates that could be the reason of the fluorescence quenching.

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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, robust, and nonradioactive approach for exploring N-myristoylation

Myristoyl-CoA (CoA): protein N-myristoyltransferase (NMT) catalyzes protein modification through covalent attachment of a C14 fatty acid (myristic acid) to the N-terminal glycine of proteins, thus promoting protein-protein and protein- membrane interactions. NMT is essential for the viability of numerous human pathogens and is also up-regulated in several tumors. Here we describe a new, nonradioactive, ELISA-based method for measuring NMT activity. After the NMT-catalyzed reaction between a FLAG-tagged peptide and azido-dodecanoyl-CoA (analog of myristoyl-CoA), the resulting azido-dodecanoyl-peptide-FLAG was coupled to phosphine- biotin by Staudinger ligation, captured by plate-bound anti-FLAG antibodies and detected by streptavidin-peroxidase. The assay was validated with negative controls (including inhibitors), corroborated by HPLC analysis, and demonstrated to function with fresh or frozen tissues. Recombinant murine NMT1 and NMT2 were characterized using this new method. This versatile assay is applicable for exploring recombinant NMTs with regard to their activity, substrate specificity, and possible inhibitors as well as for measuring NMT-activity in tissues. Copyright

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