Discovery of Pd2(DBA)3

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Stereoselective construction of various O-glycosidic bonds was first achieved by different palladium sources using 3,4-O-carbonate galactal as the donor to reach yields up to 95% under mild conditions. With Pd(II) catalyst coordination of this glycal donor from the beta-face directed by carbonate group, hard nucleophiles (aliphatic alcohols) gave beta-glycosides and alpha-glycosides were obtained from soft nucleophiles (phenols). In contrast, with the Pd(0) catalyst coordinating the donor from the beta-face due to steric effect, both hard and soft acceptors could only generate beta-glycosides via hydrogen-bond-mediated aglycone delivery.

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

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This review summarizes the state of knowledge on the chemical methods of C(5)-modifications of uridine and cytidine derivatives and may serve as a useful tool for synthetic chemists to choose an appropriate reaction protocol. The synthesis of 5-substituted uracil derivatives is gaining an increasing interest because of their possible applications in medicine and pharmacy. Modifications at the C(5) position of pyrimidine nucleosides can enhance their biostability, bioavailability or(and) biological activity. Among the C(5)-modified nucleosides, 5-halopyrimidines exhibit anticancer, antiviral, radio- and photosensitizing properties. Besides 5-halo-substituted derivatives, there are other examples of nucleosides with confirmed biological activity containing a C-C bond at the C(5) position in the pyrimidine ring. In recent decades, scientists have achieved great progress in the field of cross-coupling reactions. Among them, nickel-catalyzed processes provide a broad spectrum of synthetic methods that are based on less toxic and cheaper starting materials. This review summarizes the synthetic approaches based on the coupling or halogenation reactions, which enable 5-substituted pyrimidine nucleosides to be obtained. Moreover, the importance of the systems considered for medicine and pharmacy is briefly discussed. The bibliography includes 197 references.

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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 practical preparation of the reagent PMDTALi using a super base system under mild conditions has been developed. This PMDTALi base has been demonstrated to be a very efficient reagent for the lithiation of bridged alkenes via direct deprotonation. Further reactions with electrophiles and also coupling reactions in the presence of Pd catalysts provide the bridged alkenes with a broad range of functional groups including silyl, alkyl, halogen and aryl substituents. The utilization of this new lithium reagent has brought a new diversity to the choice of lithium reagent for the deprotonation of synthetically challenging systems.

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

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Cyclic ether pyrazol-4-yl-heterocyclyl-carboxamide com­pounds of Formula I, including stereoisomers, geometric iso­mers, tautomers, and pharmaceutically acceptable salts thereof, wherein R2 is a cyclic ether andX is thiazolyl, pyrazinyl, pyridinyl, or pyrimidinyl, are useful for inhibiting Pim kinase, and for treating disorders such as cancer mediated by Pim kinase. Methods of using compounds of Formula I for in vitro, in situ, and in vivo diagnosis, prevention or treatment of such disorders in mammalian cells, or associated pathologi­cal conditions, are disclosed

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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 purely organic and high-spin polyradical molecule was synthesized, along the non-Kekule and non-disjoint design of the pi-conjugated poly(1,2-phenylenevinylene) backbone pendantly 4,6-substituted with the robust arylaminium radicals. 4,6-Bis(bis(4-methoxyphenyl)amino)-2-bromostyrene was synthesized and polymerized with a Pd-phosphine catalyst to afford the head-to-tail linked polyradical precursor. Oxidation of the polymer with SbCl5 gave the aminium polyradical with a half-life of >10 days at room temperature. A high-spin ground state with an average S = 5/2 for this polyradical was proved by magnetic susceptibility and ESR.

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

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We have studied the synthesis of palladium nanoparticles over carbon nanotubes (Pd/CNT) and graphene (Pd/G) and we have tested their catalytic performance in the liquid phase chemoselective hydrogenation of para-chloronitrobenzene at room temperature. The catalysts were characterized by N2 adsorption/desorption isotherms, TEM, X-ray diffraction, infrared and X-ray photoelectron spectroscopy and ICP-OES. The palladium particle size on Pd/G (3.4 nm) and Pd/CNT (2.8 nm) was similar though the deposition was higher on Pd/G. Pd/CNT was more active which can be ascribed to the different surface area and electronic properties of the Pd nanoparticles over CNT, while the selectivity was 100% to the corresponding haloaniline over both catalysts and they were quite stable upon recycling.

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

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Catalytic carbon-carbon bond formation based on cross-coupling reactions plays a central role in the production of natural products, pharmaceuticals, agrochemicals and organic materials. Coupling reactions of a variety of organometallic reagents and organic halides have changed the face of modern synthetic chemistry. However, the high reactivity and poor selectivity of common organolithium reagents have largely prohibited their use as a viable partner in direct catalytic cross-coupling. Here we report that in the presence of a Pd-phosphine catalyst, a wide range of alkyl-, aryl- and heteroaryl-lithium reagents undergo selective cross-coupling with aryl- and alkenyl-bromides. The process proceeds quickly under mild conditions (room temperature) and avoids the notorious lithium halogen exchange and homocoupling. The preparation of key alkyl-, aryl- and heterobiaryl intermediates reported here highlights the potential of these cross-coupling reactions for medicinal chemistry and material science.

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

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In this study, three random copolymers including quinoxaline derivatives with different substituent groups, 2,6-bis(trimethylstannyl)-4,8-bis(2-ethylhexyloxy)benzo[1,2-b:4,5-b?]dithiophene and 4,7-dibromo-2-(2-octyldodecyl)-2H-benzo[d][1,2,3]triazole, were designed and synthesized according to the donor-acceptor (D-A) approach. 1H NMR spectroscopy, UV-Vis absorption spectroscopy, cyclic voltammetry, and gel permeation chromatography were utilized for the characterization of the polymers. Optical studies were performed in order to investigate the absorption behaviors of the polymers. P1, P2 and P3 demonstrate broad visible light absorption behavior with maximum absorption peaks around 374/539, 493/535 and 488/532 nm and their optical band gap values were calculated as 1.74, 1.87 and 1.70 eV respectively. Bulk heterojunction photovoltaic devices were fabricated using the synthesized polymers as electron donors with fullerene derivatives where the best power conversion efficiencies were found to be 2.03% for P1 : PC71BM (1 : 3, w : w), 2.22% for P2 : PC71BM (1 : 4, w : w) and 1.52% for P3 : PC71BM (1 : 2, w : w) with methanol treatment.

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

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Abstract Two new palladium-catalyzed reactions of aromatic sulfur compounds enabled the conversion of dibenzothiophenes into triphenylenes in four steps. This transformation of one aromatic framework into another consists of 1) 4-chlorobutylation of the dibenzothiophene to form the corresponding sulfonium salt, 2) palladium-catalyzed arylative ring opening of the sulfonium salt with a sodium tetraarylborate, 3) an intramolecular SN2 reaction to form a teraryl sulfonium salt, and 4) palladium-catalyzed intramolecular C-S/C-H coupling through electrophilic palladation. Symmetrical as well as unsymmetrical triphenylenes of interest were synthesized in a tailor-made fashion in satisfactory overall yields. A change of heart: The invention of two palladium-catalyzed arylation reactions of organosulfur compounds enabled the transformation of dibenzothiophenes into triphenylenes and thus a fundamental change in the core aromatic structure (see scheme). Both symmetrical and unsymmetrical triphenylenes were synthesized in a tailor-made fashion in satisfactory overall yield.

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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 provides agents for treating or preventing diseases such as mood disorder, anxiety disorder, schizophrenia, Alzheimer’s disease, Parkinson’s disease, Huntington’s chorea, eating disorder, hypertension, gastrointestinal disease, drug addiction, epilepsy, cerebral infarction, cerebral ischemia, cerebral edema, head injury, inflammation, immune-related disease, alopecia. Specifically, the invention provides fused azole derivatives represented by general formula (I) or pharmaceutically acceptable salts thereof that have an antagonistic action against the arginine-vasopressin 1b receptor:

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