Brief introduction of Pd2(DBA)3

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POSITIVE ALLOSTERIC MODULATORS OF MGLUR2

The disclosure generally relates to compounds of formula I, including their salts, as well as compositions and methods of using the compounds. The compounds modulate the mGluR2 receptor and may be useful for the treatment of various dis-orders of the central nervous system

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

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Synthesis of Chiral-Bridged Atropisomeric Monophosphine Ligands with Tunable Dihedral Angles and their Applications in Asymmetric Suzuki?Miyaura Coupling Reactions

Precise chiral recognition was firstly realized in the construction of diastereomeric biaryl monophosphines by means of the substrate-directed asymmetric annulation reactions. A series of new chiral-bridged atropisomeric biphenyl monophosphine ligands with tunable dihedral angles was accordingly synthesized successfully without a resolution step being needed. Using these ligands, different kinds of axially chiral 1,1?-biaryl-2-phosphonates including the first reported quinolyl biaryl phosphonates were prepared in 42?97% yields with up to 96% ee via palladium-catalyzed asymmetric Suzuki coupling reactions. (Figure presented.).

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

The important role of Pd2(DBA)3

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Reactivity of Planar-Chiral alpha-Ferrocenyl Carbocations towards Electron-Rich Aromatics

The reaction of the enantiopure, planar-chiral alpha-ferrocenyl carbocation (Sp)-2-(P(=S)Ph2)FcCH2+ (Fc = Fe(eta5-C5H5)(eta5-C5H3)) towards electron-rich arenes C6H5E (E = NH2, NMe2, NiPr2, NPh2, PPh2, P(=S)Ph2, OH, SH, SMe) regarding either a nucleophilic attack of the group E or an electrophilic aromatic substitution reaction of the arene at the CH2+ unit is reported. It was found that the amino, oxo or thio functionalities gave the respective ferrocenes in various product distributions, while the P-based species didn’t. Appropriate thiophosphine derivatives could be reduced to their PIII species that were applied as supporting ligands in atropselective C,C cross-coupling reactions for the synthesis of sterically hindered biaryls, where sandwich compound (Sp)-1-(PPh2)-2-(o-NMe2-C6H4)CH2-Fc gave an ee of 69 % (1 mol-% [Pd]), which is up to date the highest observed value for planar-chiral ferrocenes. The absolute configuration of the chiral ferrocenes was confirmed by single-crystal X-ray diffraction analysis. For seleno phosphane 1-(P(=Se)Ph2)-2-(CH2OH)-Fc a unique Se single-atom transfer occurred within its reaction with Sanger’s reagent. The presence of two chemically different Se atoms in 1-(P(=Se)Ph2)-2-(((2,4-(NO2)2-C6H3)Se)CH2)-Fc was confirmed by 77Se{1H} NMR spectroscopy and single-crystal X-ray diffraction analysis, respectively.

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

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Enantioselective palladium(0)-catalyzed nazarov-type cyclization

A Pd0-catalyzed asymmetric Nazarov-type cyclization is described. The optimized ligand for the reaction incorporates a weakly coordinating pyridine ring into a TADDOL-derived phosphoramidite (TADDOL=alpha,alpha,alpha,alpha-tetraaryl-1,3-dioxolane-4,5-dimethanol). The reaction leads to the formation of cyclopentenones as single diastereoisomers that incorporate two contiguous asymmetric centers, one tertiary and one an all-carbon-atom quaternary stereocenter, in high yield and optical purity. It is noteworthy that the reaction does not require that substrates should be activated by aryl substituents.

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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 chloroethoxylation of aromatic and heteroaromatic chlorides: An orthogonal functionalization of a chloroethoxy linker

A novel disconnection based on cross-coupling chemistry was designed to access pharmaceutically relevant aryl-aminoethyl ethers. The developed palladium-catalyzed functionalization of aryl- and heteroaryl chlorides with a sodium tetrakis-(2-chloroethoxy) borate salt is orthogonal to the simple nucleophilic replacement of the chloro function of the ethylene linker. The transformation enables efficient 2-chloroethoxylation in the absence of an additional external base. Subsequent amine substitution of the alkyl halide affords 2-aminoethoxy arenes. The applicability of this method was demonstrated through the synthesis of various aryl- and heteroaryl-alkyl ethers, including the intermediates of marketed drug molecules.

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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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Discovery of a novel B-cell lymphoma 6 (BCL6)-corepressor interaction inhibitor by utilizing structure-based drug design

B-cell lymphoma 6 (BCL6) is a transcriptional repressor that can form complexes with corepressors via protein-protein interactions (PPIs). The complexes of BCL6 and corepressors play an important role in the formation of germinal centers (GCs), and differentiation and proliferation of lymphocytes. Therefore, BCL6-corepressor interaction inhibitors would be drug candidates for managing autoimmune diseases and cancer. Starting from high-throughput screening hits 1a and 2a, we identified a novel BCL6-corepressor interaction inhibitor 8c (cell-free enzyme-linked immunosorbent assay [ELISA] IC50=0.10muM, cell-based mammalian two-hybrid [M2H] assay IC50=0.72muM) by utilizing structure-based drug design (SBDD) based on an X-ray crystal structure of 1a bound to BCL6. Compound 8c also showed a good pharmacokinetic profile, which was acceptable for both in vitro and in vivo studies.

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

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Enhancing the photovoltaic properties of low bandgap terpolymers based on benzodithiophene and phenanthrophenazine by introducing different second acceptor units

Two novel donor-acceptor (D-A) type random conjugated terpolymers PBDTT-PPzIID and PBDTT-PPzDPP were synthesized by copolymerizing electron-rich alkylthienyl benzodithiophene (BDTT) and two different electron-deficient units, in which phenanthrophenazine (PPz) was the first acceptor unit, and isoindigo (IID) or diketopyrrolopyrrole (DPP) with a strong electron-withdrawing ability was the second acceptor unit, respectively. Compared to their parent polymer PTTPPz-BDTT, a broadening of the band in the long wavelength region from 500 to 850 nm and a significant decrease in HOMO levels were observed for the random terpolymers. Ca and PFN-Br were used as interfacial layers to optimize the devices, respectively. Pleasingly, after replacing Ca/Al with PFN-Br/Al as the cathode, the performance of both polymer devices improved greatly. A maximum power conversion efficiency (PCE) of 5.91% was obtained with a Voc of 0.73 V, a Jsc of 11.75 mA cm-2 and a FF of 68.8% in the PBDTT-PPzDPP/PC71BM-based device, while the PBDTT-PPzIID/PC71BM-based device achieved a PCE of 4.21%. To the best of our knowledge, this is one of the highest recorded FF values among PSCs based on previously reported phenazine copolymers.

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

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Synthesis of oligodeoxynucleotides containing a C8-2?-deoxyguanosine adduct formed by the carcinogen 3-nitrobenzanthrone

This unit describes the detailed procedure in five parts for the synthesis of the C8-27?-deoxyguanosine-3-aminobenzanthrone adduct located in a desired site in an oligonucleotide. The synthesis of the protected 2?-deoxyguanosine, O6- benzyl-N2-DMTr-3?-5?-bisTBDMS-C8-Br-2?-deoxyguanosine, is described in the first part. The synthesis of the reduced carcinogen 3-aminobenzanthrone is detailed in part two. The third part outlines the key step of the adduct formation between the reduced carcinogen and the protected nucleoside by a palladiumcatalyzed cross coupling reaction. The final two parts describe phosphoramidite synthesis from the nucleoside-carcinogen adduct followed by its site-specific incorporation intoDNAby solid-phase oligonucleotide synthesis. The adducted oligonucleotides are purified by reversed-phase HPLC and characterized by mass spectrometry.

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

The important role of Pd2(DBA)3

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Random copolymers containing tetrafluorophenylene unit with deep HOMO energy levels for solar cell applications

Two Novel terpolymers poly{4,8-di(2-ethylhexyloxyl)benzo[1,2-b:4.5-b’]dithiophene-3,6-bis-(thiophen-2-yl)-N,N’-bis(2-octyl-1-dodecyl)-1,4-dioxo-pyrrolo[3,4-c]pyrrole-co-2,6-ditetrafluorophenyl-4,8-di(2-ethylhexyloxyl)benzo[1,2-b:4.5-b’]dithiophene} (PBDT-DPP-TFB) are designed and synthesized as donor materials in PSCs by incorporation of tetrafluorophenylene (TFB) unit with different mole ratio of 1% and 5%, namely PBDT-DPP-TFB1% and PBDT-DPP-TFB5%. It is found that through the introduction of small amount tetrafluorophenylene (TFB) into the BDT-DPP backbone, absorbance range, energy levels, the charge carrier mobility and the device performance are significantly manipulated and enhanced. Lower HOMO energy levels are emphasized for PBDT-DPP-TFB1% (?5.39?eV) and PBDT-DPP-TFB5% (?5.43?eV) compared to pristine PBDT-DPP without TFB unit, due to the strong electron-withdrawing feature of the TFB. Thanks to the more suitable energy levels, and a more favorable morphology with improved excitons dissociation and charge transport in the active layer, the inverted device based on PBDT-DPP-TFB with 1% TFB achieves a dramatic improved PCE of 2.9% with about 200% enhancement to the device with the pristine PBDT-DPP. This work demonstrates the potential of TFB in developing new organic materials for optoelectronic devices, as well as the variation of the third component can be another way to construct D-A polymers with favorable properties.

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

Extended knowledge of Pd2(DBA)3

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Synthesis and biological screening of pyrimidine linked benzene sulfonamide derivatives

Background: It has been developed a new combination of Palladium catalyzed Buchwald-Hartwig type reaction for the synthesis of N-tert-Butyl- 3- {[5- methyl- 2- (arylamino)pyrimidin- 4- yl]amino}benzene-sulfonamides 5 by the treatment of N-tert-butyl-3-[(2-chloro-5-methyl pyrimidin-4-yl)-amino]benzene sulfonamide 4 with various aromatic amines in the presence of Cs2CO3 and in DMF under microwave conditions. Method: All the eight compounds 5a-h were screened in-vitro for their antibacterial Gram-positive bacteria namely, Bacillus subtilis, Bacillus sphaericus and Staphylococcus aureus and three Gram-negative bacteria Pseudomonas aeruginosa, Klebsiella aerogenes, Chromobacterium violaceum. All the synthesized compounds were tested for their antifungal activity against five test organisms, Aspergillus Niger, Chrysosporium tropicum, Rhizopus oryzae, Fusarium moniliforme and Curvularia lunata. Results: Among the title compounds 5d and 5e exhibited potent activity towards both gram positive and gram negative bacteria. Compounds 5e and 5f showed good antifungal activity. Conclusion: A new efficient catalyst/ligand combination was developed for the synthesis of title compounds 5a-5h under microwave conditions. The microwave procedure is slightly superior to the conventional method in terms of reduced time period and better yields.

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