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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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Reference£º
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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Reference£º
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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Reference£º
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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Reference£º
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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Reference£º
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

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Efficient Pd-Catalyzed Allene Synthesis from Alkynes and Aryl Bromides through an Intramolecular Base-Assisted Deprotonation (iBAD) Mechanism

An optimized ligand-controlled palladium-catalyzed allene synthesis starting from alkynes and aryl bromides giving rise to allene products in a simple and direct manner is described. The methodology is performed in an inter- and intramolecular fashion with unprecedented scope and excellent yields. Based on mechanistic investigations and on DFT calculations, the role played by the carboxylic additive (i.e., PivOH) in controlling the selectivity of the reaction is discussed, allowing us to propose an intramolecular base-assisted deprotonation (iBAD) mechanism for this process.

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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 desulfitative arylation of 3-haloquinolines with arylsulfinates

3-Haloquinolines can be functionalized via a palladium-catalyzed desulfitative coupling of arylsulfinates. This method tolerates substitution upon the aromatic ring and shows good selectivity toward variously substituted aromatic rings. Copyright

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