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PdCl2-catalyzed efficient allylation and benzylation of heteroarenes under ligand, base/acid, and additive-free conditions

We present a PdCl2-catalyzed protocol for highly efficient allylation and benzylation of a rich variety of N-, O-, and S-containing heteroarenes under base/acid, additive, and ligand-free conditions. The method represents the very few examples for simple, universally applicable, clean, and atom-efficient functionalization of heteroarenes.

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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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Ladder-type oligo- p -phenylene-containing copolymers with high open-circuit voltages and ambient photovoltaic activity

Four ladder-type oligo-p-phenylene containing donor-acceptor copolymers were designed, synthesized, and characterized. The ladder-type oligo-p-phenylene was used as an electron donor unit in these copolymers to provide a deeper highest occupied molecular orbital (HOMO) level for obtaining polymer solar cells with a higher open-circuit voltage, while 4,7-dithien-2-yl-2,1,3- benzothiadiazole or 5,8-dithien-2-yl-2,3-diphenylquinoxaline was chosen as an electron acceptor unit to tune the electronic band gaps of the polymers for a better light harvesting ability. These copolymers exhibit field-effect mobilities as high as 0.011 cm2/(V s). Compared to fluorene containing copolymers with the same acceptor unit, these ladder-type oligo-p-phenylene containing copolymers have enhanced and bathochromically shifted absorption bands and much better solubility in organic solvents. Photovoltaic applications of these polymers as light-harvesting and hole-conducting materials are investigated in conjunction with [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM) or [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM). Without extensive optimization work, a power conversion efficiency (PCE) of 3.7% and a high open-circuit voltage of 1.06 V are obtained under simulated solar light AM 1.5 G (100 mW/cm2) from a solar cell with an active layer containing 20 wt % ladder-type tetra-p-phenylene containing copolymer (P3FTBT6) and 80 wt % PC61BM. Moreover, a high PCE of 4.5% was also achieved from a solar cell with an active layer containing 20 wt % P3FTBT6 and 80 wt % PC 71BM.

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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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Palladium-catalyzed 2,2,2-trifluoroethylation of organoboronic acids and esters

Trifluoroethylation: Aryl boronic acids can be catalytically trifluoroethylated with the readily available reagent CF3CH 2I (see scheme, dba=dibenzylideneacetone). The reaction tolerates a variety of functional groups and can be extended to the trifluoroethylation of aryl or alkenyl boronic esters. The method is also suitable for the late-stage installation of the CF3CH2 group into target molecules. Copyright

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

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CYCLOCARBAMATE DERIVATIVE AS PROGESTERONE RECEPTOR MODULATORS

This invention provides compounds of Formula (I): wherein R1 and R2 may be single substituents or fused to form spirocyclic or hetero-spirocyclic rings; R3 is H, OH, NH2, C1 to C6 alkyl, substituted C1 to C6 alkyl, C3 to C6 alkenyl, substituted C1 to C6 alkenyl, alkynyl, or substituted alkynyl, CORC; RC is H, C1 to C 3 alkyl, substituted C1 to C3 alkyl, aryl, substituted aryl, C1 to C3 alkoxy, substituted C1 to C 3 alkoxy, C1 to C3 aminoalkyl, or substituted C1 to C3 aminoalkyl; R4 is H, halogen, CN, NO2, C1 to C6 alkyl, substituted C1 to C6 alkyl, alkynyl, or substituted alkynyl, C1 to C6 alkoxy, substituted C1 to C6 alkoxy, amino, C1 to C6 aminoalkyl, or substituted C1 to C6 aminoalkyl; and R5 is selected from a trisubstituted benzene ring of a five or six membered ring with 1, 2, or 3 heteroatoms from the group including O, S, SO, SO 2 or NR6 and containing one or two independent substituents from the group including H, halogen, CN, NO 2, amino, and C1 to C3 alky, C1 to C3 alkoxy, C1 to C3 aminoalkyl, CORF, or NRGCORF; or pharmaceutically acceptable salt thereof, as well as pharmaceutical compositions and methods using the compounds as antagonists of the progesterone receptor.

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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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Controlling electron transfer in donor-bridge-acceptor molecules using cross-conjugated bridges

Photoinitiated charge separation (CS) and recombination (CR) in a series of donor-bridge-acceptor (D-B-A) molecules with cross-conjugated, linearly conjugated, and saturated bridges have been compared and contrasted using time-resolved spectroscopy. The photoexcited charge transfer state of 3,5-dimethyl-4-(9-anthracenyl)julolidine (DMJ-An) is the donor, and naphthalene-1,8:4,5-bis(dicarboximide) (NI) is the acceptor in all cases, along with 1,1-diphenylethene, trans-stilbene, diphenylmethane, and xanthone bridges. Photoinitiated CS through the cross-conjugated 1,1-diphenylethene bridge is about 30 times slower than through its linearly conjugated trans-stilbene counterpart and is comparable to that observed through the diphenylmethane bridge. This result implies that cross-conjugation strongly decreases the pi orbital contribution to the donor-acceptor electronic coupling so that electron transfer most likely uses the bridge sigma system as its primary CS pathway. In contrast, the CS rate through the cross-conjugated xanthone bridge is comparable to that observed through the linearly conjugated trans-stilbene bridge. Molecular conductance calculations on these bridges show that cross-conjugation results in quantum interference effects that greatly alter the through-bridge donor-acceptor electronic coupling as a function of charge injection energy. These calculations display trends that agree well with the observed trends in the electron transfer rates.

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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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Suzuki-Miyaura homocoupling of naphthyl triflates using bis(pinacolato)diboron: Approaches to the biaryl skeleton of crisamicin A

Homocoupling of naphthyl triflates 27, 16, 17 to the respective binaphthyls 28, 31 and 35 has been achieved in a one-pot procedure using bis(pinacolato)diboron and PdCl2(dppf). Use of potassium acetate as the base provides access to the initial naphthylboronate intermediates whereas the stronger base potassium phosphate is required in order to promote subsequent coupling of the naphthylboronate with a second equivalent of the naphthyl triflate. Attempts to convert binaphthyl 35 into bis-acetylnaphthalene 14, a key intermediate for the synthesis of the dimeric pyranonaphthoquinone antibiotic crisamicin A 2, via double Fries rearrangement of bis-acetate 37 derived from binaphthyl 35, were unsuccessful. Attempts to introduce the acetyl groups at C-7 and C-7? on bis-acetylnaphthalene 14 via Fries rearrangement of the monomeric precursors 21 and 15, before effecting homocoupling to a biaryl were unsuccessful. Introduction of an acetyl group via initial bromination ortho to the hydroxyl group in naphthol 18, which bears an electron rich benzyl ether at C-7, was plagued by the formation of phenolic coupling product 42 and naphthoquinone 43. Bromination of naphthol 45, bearing a less electron rich triflate group at C-7, also afforded binaphthol 47 resulting from phenolic coupling as well as naphthoquinone 48 when using N-bromosuccinimide at low temperature.

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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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PYRROLE AMIDE INHIBITORS

The present invention provides for compounds of formula (I) wherein R1, R2, R3, and R10 have any of the values defined in the specification, and pharmaceutically acceptable salts thereof, that are useful as agents in the treatment of diseases and conditions, including inflammatory diseases, cancer, and AIDS. Also provided are pharmaceutical compositions comprising one or more compounds of formula (I).

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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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Carbocyclic compounds useful as leukotriene antagonists

This invention comprises novel carbocyclic compounds of formula I (wherein A, Z, R11 and R12 are defined in the specification) derived from acylsulfonamide derivatives of alpha-carbocyclyltoluic acids wherein said compounds of formula I antagonize the actions of one or more of the arachidonic acid metabolites known as leukotrienes. The invention also provides pharmaceutically acceptable salts of the formula I compounds; pharmaceutical compositions containing the formula I compound, or their salts, for use in the treatment of, for example, allergic or inflammatory diseases, or endotoxic or traumatic shock conditions; and processes for the manufacture of the formula I compounds, as well as intermediates for use in such manufacture.

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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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Ethylzincation of monosubstituted alken es catalyzed by EtMgBr-Cl2ZrCp2 and palladium-catalyzed cross coupling of the resultant diisoalkylzinc derivatives

The reaction of monosubstituted alkenes with 0.5 molar equiv of EtZn in the presence of a catalyst generated in situ by treatment ofClzZrCpz with 2 molar equiv of EtMgBr produces regioselectively the corresponding diisoalkylzincs 1, generally in high yields. Their direct cross coupling with a variety of organic halides in the same reaction vessel can be achieved in good yields with a catalytic amount of a palladium complex.

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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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Total synthesis of spirastrellolide A methyl ester – Part 1: Synthesis of an advanced C17-C40 bis-spiroacetal subunit

Out of the blue: The marine macrolide spirastrellolide A is a potent and selective inhibitor of protein phosphatase 2A and a lead for anticancer therapies. A flexible and modular synthetic strategy has been developed with two routes for the construction of the DEF bis-spiroacetal subunit. The optimized Suzuki coupling approach results in the efficient preparation of a C17-C40 aldehyde that forms the cornerstone of the first total synthesis. (Chemical Equation Presented).

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