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This invention relates to novel 1-cycloalkyl- or 1-heterocyclyl-hydroxyimino-3-phenyl-propanes of the formula wherein R1 to R7 are as defined in the description and in the claims, as well as pharmaceutically acceptable salts thereof. These compounds are GPBAR1 agonists and may therefore be useful as medicaments for the treatment of diseases such as type II diabetes.

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

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Star-shaped pi-extended molecules comprising discotic aromatic cores and peripheral pi-conjugated arms have attracted significant attention as diverse optoelectronic materials in terms of their large pi-surface, tunable self-assembly, enhanced charge transport and fluorescence, and liquid crystallinity. Although many efforts have been made in the construction of various aromatic discotic cores, a new class of C3-symmetric star-shaped discotic pi-molecules consisting of electron-deficient benzotristhiazole and benzotrisoxazole cores, which are expected to exhibit distinct optoelectronic properties, remains unexplored owing to the unachievable synthetic approaches involved in their synthesis. Herein, we report a novel and highly efficient Pd-catalyzed cyclotrimerization of the functionalized thiazoles or oxazoles for the construction of a new class of discotic molecules of benzotristhiazole and benzotrisoxazole central cores with star-shaped pi-conjugated arms. The combination of [Pd2(dba)3]/XPhos (dba=dibenzylideneacetone) catalyst systems with the 4-bromo-substituted thiazole enables the formation of a sufficiently stable thiazole?Pd species that participates in the subsequent C?H arylations consecutively to form the corresponding cyclic trimer products. This new class of star-shaped discotic pi-extended products showed tunable energy levels and high fluorescence quantum yields that make them promising candidates for optoelectronic applications.

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

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Isoindigo-based copolymers containing non-fluorinated (PIIDBT) and fluorinated bithiophene moieties (PIIDFBT) were synthesized. The replacement of hydrogen atoms with electronegative fluorine atom attained the intramolecular noncovalent interactions in conjugated polymer structure employing the concept of conformational locks. Furthermore, the fluorine characteristics as substituent atoms tuned the electron withdrawing ability and made the HOMO energy levels of fluorinated moieties deeper (-5.79 eV) than that of non-fluorinated polymer (-5.54 eV). As a result, the photovoltaic performance of PIIDFBT was improved by increasing its open circuit voltage (Voc) up to 1.01 V, resulting in a power conversion efficiency of 6.21%. The PIIDFBT with high Voc can be recognized as a promising candidate for both single junction and multi-junction photovoltaics.

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

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An anthranilic acid derivative represented by the general formula (X) [wherein R1 represents hydrogen or a carboxy-protecting group; R2 represents optionally substituted phenyl, a heterocyclic group, etc.; R3 repre- sents optionally substituted phenyl, a monocyclic hete- rocyclic group, etc.; X1 represents carbonyl, etc.; X2 rep- resents optionally substituted alkylene group, a bond, etc.; X3 represents oxygen, a bond, etc.; and X4 represents a group represented by the general formula -X5-X6- or -X6-X5- (wherein X5 means oxygen, a bond, etc.; and X6 means optionally substituted alkylene, a bond, etc.)] or a salt of the derivative. The derivative or salt has the inhibitory activity of MMP-13 production and is hence useful as a therapeutic agent for articular rheumatism, osteoarthritis, cancer, etc

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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 paper describes the synthesis of a cyclophosphazene-based diphenylphosphine ligand and a new Pd(0) complex. Infrared spectroscopy (ATR-IR), ESI+-MS, 31P, 1H and 13C NMR, Raman, WD-XRF, ICP-OES and TGA analysis show the coordination of two palladium atoms per unit of cyclophosphazene. A semiempirical calculation method was employed to find the lowest energy structure among the possible ones and Density Functional Theory (DFT) was used to optimize the found structure and obtain its bond angles, dihedral angles, bond lengths, atomic distances, and to calculate the vibrational spectrum (PBE/def2-TZVP(-f)). The new Pd complex showed activity in Suzuki-Miyaura cross-coupling reactions with halobenzenes and phenylboronic acid, tolerating different functional groups.

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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 preparation and reactivity of elusive palladium proazaphosphatrane complexes that represent putative intermediates in C-N cross-coupling reactions are described. Variable transannulation in these compounds, as determined by X-ray crystallography, validates the previously untested hypothesis that proazaphosphatranes undergo conformational changes to stabilize catalytic intermediates. The competence of these complexes as catalytic intermediates is supported through stoichiometric and catalytic coupling reactions, providing the first examples of discrete proazaphosphatrane complexes employed in cross-coupling.

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

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Several Hiyama cross-coupling reactions of oxasilacycloalkenes and aryl iodides are described that produce trisubstituted Z-styrenes in moderate to excellent yields. Both electron-rich and electron-poor aryl iodides are tolerated in the cross-coupling reaction. The oxasilacycloalkene coupling partners were prepared by ruthenium-catalyzed intramolecular anti-hydrosilylation of alkynols. One of the cross-coupling products was converted to a 1-benzoxocane, albeit in low yield, using an intramolecular Buchwald-Hartwig etherification. The cyclic ether produced contains the carbon skeleton of heliannuol A.

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

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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