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Large branched alkylthienyl bridged naphtho[1,2-c:5,6-c?]bis[1,2,5]thiadiazole-containing low bandgap copolymers: Synthesis and photovoltaic application

Two donor-acceptor (D-A) type low bandgap (LBG) alternating conjugated copolymers containing larger conjugation planarity and stronger electro-withdrawing ability naphtho[1,2-c:5,6-c?]bis[1,2,5]thiadiazole (NT) unit, namely, poly[4,8-bis(5-(n-octylthio)thien-2-yl)-benzo[1,2-b:4,5-b?]dithiophene-2,6-diyl-alt-4,9-bis(4-(2-decyltetradecyl)thien-2-yl)naphtho- [1,2-c:5,6-c?]bis[1,2,5]thiadiazole-5,5?-diyl] (PBDT-TS-DTNT-DT) and poly[4,8-bis(triiso-propylsilylethynyl)benzo[1,2-b:4,5-b?]dithiophene-2,6-diyl-alt-4,9-bis(4-(2-decyltetradecyl)-thien-2-yl)naphtho[1,2-c:5,6-c?]bis[1,2,5]thiadiazole-5,5?-diyl] (PBDT-TIPS-DTNT-DT), were prepared by the palladium-catalyzed Stille polycondensation and characterized by gel permeation chromatography (GPC), UV-Vis absorption, thermal gravimetric analysis (TGA), cyclic voltammetry (CV) etc. PBDT-TS-DTNT-DT and PBDT-TIPS-DTNT-DT show the broader absorption and deeper highest occupied molecular orbital (HOMO) energy level approximately ?5.45 and ?5.62?eV, respectively. Bulk-heterojuction solar cells based on the resulted polymers and [6,6] phenyl-C61 butyric acid methyl ester (PC61BM) blends, with the device configuration of ITO/PFN/polymer:PC61BM/MoO3/Ag were prepared and investigated. The results showed the power conversion efficiency (PCE) of 2.67% for PBDT-TS-DTNT-DT/PC61BM (w:w, 1:2) and 0.64% for PBDT-TIPS-DTNT-DT/PC61BM (w:w, 1:1), with relatively high open-circuit voltage (VOC) of 0.86 and 1.05?V, small short-circuit current (JSC) of 5.41 and 0.97?mA cm?2 and moderate fill factor (FF) of 57.8% and 62.4%, under an AM1.5 simulator (100?mWcm?2), respectively.

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

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Regiocontrolled palladium-catalyzed arylative cyclizations of alkynols

Tuning the reactivity of arylpalladium intermediates enables control of catalytic arylative 5-exo and 6-endo cyclizations of alkynols. The two modes of cyclizations represent a rare example of controllable, regioselective difunctionalization of alkynes. The cyclizations are useful in offering a divergent synthesis of oxygen-containing heterocycles, which is of synthetic use for further derivatization. Formal synthesis of an hNK-1 receptor antagonist also showcases the utility of our arylative cyclization.

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

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Vinylidenation of Organoboronic Esters Enabled by a Pd-Catalyzed Metallate Shift

Organoboron ?ate? complexes undergo a net vinyl insertion reaction to give 1,1-disubstituted alkenyl boronic esters when treated with stoichiometric allyl acetate and a palladium catalyst. Reactions that employ vinyllithium afforded good to excellent yields after one hour, while reactions that employ vinylmagnesium chloride furnished modest to good yields after 18 hours.

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

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Highly Modular Synthesis of 1,2-Diketones via Multicomponent Coupling Reactions of Isocyanides as CO Equivalents

A one-pot, four-component Pd-catalyzed coupling has been developed for the synthesis of unsymmetrical 1,2-diketones from aryl halides and alkyl zincs employing tert-butyl isocyanide as a CO source. The intermediate 1,2-diketones have been elaborated to quinoxalines. Mechanistic studies help to rationalize the high selectivity for the bis- vs monoinsertion product.

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

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Ortho-(Dimesitylboryl)phenylphosphines: Positive boryl effect in the palladium-catalyzed suzuki-miyaura coupling of 2-chloropyridines

Catalytic systems combining ortho-(dimesitylboryl) phenylphosphines and palladium precursors have been evaluated in the Suzuki-Miyaura couplings of chloro-N-heterocycles, in particular 2-chloro pyridines, with arylboronic acids. The Lewis basic character of the substrates does not interfere with the Lewis acidic site of the ligands, even for a substrate featuring free NH2 groups. The influence of several reaction parameters has been studied and the ortho-dimesitylboryl moiety was actually found to substantially enhance the catalytic performance. The role of this group has been examined using preformed phosphine-borane/Pd complexes and the formation of an original phosphine/h4-boratabutadiene complex has been identified as a possible deactivation pathway. Regioselective coupling of 2,6-dichloro-3-nitropyridine with phosphine-borane/Pd catalysts has also been explored, and sequential double cross-couplings were found to give a direct and efficient access to unsymmetrical 2,6-diarylpyridines.

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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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Substituted Phenylamino-Pyrimidines

The invention relates to substituted phenylaminopyrimidines, to a process for their preparation and to their use for preparing medicaments for the treatment and/or prophylaxis of diseases in humans and animals, in particular cardiovascular disorders.

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

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High triplet energy crosslinkable hole transport material for blue phosphorescent organic light-emitting diodes

A high triplet energy crosslinkable hole transport material was developed for solution processed blue phosphorescent organic light-emitting diodes. A high triplet energy core structure, 3,3-di(9H-carbazol-9-yl)biphenyl, was functionalized with a vinylbenzene crosslinking unit to form the crosslinked hole transport layer. Crosslinking of the hole transport layer at 220 C produced an insoluble film which is stable under exposure to solvents. A blue emitting layer of iridium(III) bis(2-(4,6-difluorophenyl)-pyridinato-N,C2)picolinate doped diphenyldi(4-(9-carbazolyl)phenyl)silane was spin-coated on the crosslinked hole transport layer without damaging the underlying hole transport layer, which afforded solution processed blue phosphorescent organic light-emitting diodes with an external quantum efficiency of 19.1%.

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

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Inhibitors of the 11-beta-hydroxysteroid dehydrogenase Type 1 enzyme

The present invention relates to compounds which are inhibitors of the 11-beta-hydroxysteroid dehydrogenase Type 1 enzyme. The present invention further relates to the use of inhibitors of 11-beta-hydroxysteroid dehydrogenase Type 1 enzyme for the treatment of non-insulin dependent type 2 diabetes, insulin resistance, obesity, lipid disorders, metabolic syndrome, and other diseases and conditions that are mediated by excessive glucocorticoid action.

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

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Sequential Pyridine Dearomatization-Mizoroki-Heck Cyclization for the Construction of Fused (Dihydropyrido)isoindolinone Ring Systems

Acylation of 4-alkylpyridines with 2-iodobenzoyl chlorides under basic conditions results in pyridine dearomatization via formation of 4-alkylidene dihydropyridines. These reasonably stable intermediates are further transformed through Pd-catalyzed Mizoroki-Heck cyclization to afford dihydropyrido-fused isoindolinone products in good yield. This study demonstrates successful harnessing of reactive dearomatized pyridine anhydrobases in metal-catalyzed C-C bond-forming reactions, and provides an efficient entry to isoindolinone ring systems structurally related to several indolizidine alkaloid frameworks.

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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 selective formation of substituted pyrroles from alkene-tethered cyclic oxime esters

Isoxazol-5(4H)-ones were used as nitrene precursors for the selective formation of trisubstituted pyrroles by applying a palladium-catalyzed decarboxylative ring-reconstruction method. The use of bulky biaryl-type monophosphine ligands was effective for improving the selectivity. Deuterium-labeling experiments suggested a mechanism involving beta-hydride elimination followed by reductive elimination from an aza-pi-allyl intermediate.

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