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Direct and selective mono-N-pyridylation of trans-(R,R)-cyclohexane-1,2- diamine is described here. Facile preparation of a novel chiral 2-aminoDMAP core catalaphore via Cu catalysis has led to the development of various sulfonamide/2-aminoDMAPs as bifunctional acid/base organocatalysts (most in two steps overall), which have been shown to very effectively promote asymmetric conjugate addition of acetylacetone to trans-beta-nitroolefins with good to excellent yields (87-93%) and enantioselectivites (up to 99%).

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

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Domino cyclization: Alkylpalladium intermediates in an asymmetric Heck reaction were intercepted by a second alkene to give tricyclic products with high enantioselectivity (see scheme; Boc=tert-butoxycarbonyl). The method was applied to the asymmetric synthesis of a precursor of (-)-martinellic acid, a folk eye medicine in South America. Copyright

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

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Pd-Catalyzed Autotandem Reactions with N-Tosylhydrazones. Synthesis of Condensed Carbo- and Heterocycles by Formation of a C-C Single Bond and a C-C Double Bond on the Same Carbon Atom

A new Pd-catalyzed autotandem reaction is introduced that consists of the cross-coupling of a benzyl bromide with a N-tosylhydrazone followed by an intramolecular Heck reaction with an aryl bromide. During the process, a single and a double C-C bond are formed on the same carbon atom. Two different arrangements for the reactive functional groups are possible, rendering great flexibility to the transformation. The same strategy led to 9-methylene-9H-fluorenes, 9-methylene-9H-xanthenes, 9-methylene-9,10-dihydroacridines, and also dihydropyrroloisoquinoline and dihydroindoloisoquinoline 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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Two-dimensional regioregular polythiophenes with conjugated side chains for use in organic solar cells

We have prepared two two-dimensional polythiophenes (2D-PTs; P1 and P2) possessing alkyl-thiophene side chains by Stille coupling reactions. Optical measurements indicate that the bandgaps of P1 and P2 being 1.98 and 1.77 eV, respectively. P2 displayed a red-shift in its absorption spectrum because of the longer length of its conjugated side chains. Desirable highest occupied molecular orbital (HUMO) and lowest unoccupied molecular orbital (LUMO) energy levels were obtained from electrochemical studies, which suggested that these systems would exhibit high open-circuit voltages when blended with fullerene as electron acceptors. The hole mobility (thin film transistor (TFT) measurement) of P1 and P2 are 3.5×10-4 and 4.6×10-3 cm2 V-1 s-1, respectively. A power conversion efficiency of 2.5% is obtained under simulated solar illumination (AM 1.5G, 100 mW cm-2) from a polymer solar cell comprising an active layer containing 25 wt% P1 and 75 wt% [6,6]-phenyl-C71 butyric acid methyl ester (PC71BM).

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

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Ethynyl-Linked Donor-pi-Acceptor Boron Dipyrromethenes for Panchromatic Dye-Sensitized Solar Cells

Two boron dipyrromethene (BODIPY) derivatives were prepared as functional materials for applications in dye-sensitized solar cells (DSSCs). These compounds consist of a donor-pi-acceptor skeleton in which an electron donor and an electron acceptor/anchoring group are introduced to the opposite C2 and C6 positions of a BODIPY core via an ethynyl linker (compounds DN1 and DN2). The molecular structure of one of the key intermediates (compound 8) was determined by x-ray diffraction analysis. Both compounds exhibited panchromatic absorptions in the UV/Vis region. The results of electrochemical studies revealed that the HOMO and LUMO levels of these compounds were suitable for the construction of DSSCs consisting of a TiO2 electrode and an electrolyte based on an I3 ?/I? redox couple. The optimized structures, frontier molecular orbitals, and absorption spectra of both sensitizers were calculated using density functional theory. A DSSC prepared using the benzothiadiazole-containing analogue DN2 exhibited a photovoltaic conversion efficiency of 3.41 %.

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

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Expedient Pd-Catalyzed alpha-Arylation towards Dibenzoxepinones: Pivotal Manske’s Ketone for the Formal Synthesis of Cularine Alkaloids

The general synthesis of diversely substituted dibenzoxepinones by a combined Pd-catalyzed alpha-arylation and SNAr strategy is reported and applied to the synthesis of Manske’s ketone, a key intermediate en route to the total synthesis of cularine alkaloids. In the course of this work, an unanticipated ring contraction reaction to a xanthone was observed and serves as a caveat for the conditions of the widely used alpha-arylation reaction.

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

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Palladium-Catalyzed Dearomative syn-1,4-Diamination

Herein we report a dearomative syn-1,4-diamination protocol using simple nonactivated arenes and amines. This one-pot method utilizes arene-arenophile para-cycloadducts, formed via visible-light-mediated [4+2]-photocycloaddition that undergoes formal allylic substitution with amine nucleophiles under Pd-catalysis. The products are obtained with exclusive syn-1,4-selectivity; the method permits enantioselective desymmetrization of naphthalene, as well as elaborations of amine-containing drug molecules. Furthermore, the resulting unsaturated products are amenable to numerous options for diversification. Overall, this novel dearomative functionalization strategy offers rapid and straightforward access to complex building blocks, which are difficult to prepare otherwise, from simple 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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HETEROCYCLIC COMPOUND

Provided is a compound having a superior FLAP inhibitory action and useful as a prophylactic or therapeutic agent for arteriosclerosis and the like, and a salt thereof. The present invention relates to a compound represented by the formula wherein each symbol is as defined in the present DESCRIPTION, or a salt thereof.

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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 of Formula (I): or a pharmaceutically acceptable salt thereof, corresponding pharmaceutical compositions, compound preparation and treatment methods directed to bacterial infections and inhibition of bacterial peptide deformylase (PDF) activity.

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

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Two-photon absorption properties of conjugated supramolecular porphyrins with electron donor and acceptor

Two-photon absorption (2PA) cross-section values of supramolecular porphyrin tetramer consisting of two monoacetylene-linked bisporphyrins with and without ferrocene/C60 groups as electron donor/ acceptor through the coordination of pyridyl to zinc were measured using a nanosecond open aperture Z-scan method. The maximum effective cross-section value was observed for the compound having asymmetric terminals of ferrocene and C60 as 2.0 × 105 GM. The values obtained for compounds having two C60’s, two ferrocene’s, no donor/acceptor, and stacked isomer were 1.7 × 105 GM, 1.5 × 105 GM, 1.1 × 105 GM, and 1.3 × 105 GM, respectively. These results indicate that the asymmetric donor-pi-acceptor structure is the best for 2PA enhancement for this series of molecules. These values are extremely large compared to those of unit dimer 2D (190 GM at 780 nm) and compounds reported hitherto in literatures.

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