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The methods described in this chapter concern procedures for the design, synthesis, and in vitro biological evaluation of an array of potent retinoid-X-receptor (RXR) agonists employing 6-(ethyl(5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)amino)nicotinic acid (NEt-TMN), and recently reported NEt-TMN analogs, as a case study. These methods have been extensively applied beyond the present case study to generate several analogs of other potent RXR agonists (rexinoids), particularly the RXR agonist known as bexarotene (Bex), a Food and Drug Administration (FDA) approved drug for cutaneous T-cell lymphoma that is also often prescribed, off-label, for breast, lung, and other human cancers. Common side effects with Bex treatment include hypertriglyceridemia and hypothyroidism, because of off-target activation or inhibition of other nuclear receptor pathways impacted by RXR. Because rexinoids are often selective for RXR, versus the retinoic-acid-receptor (RAR), cutaneous toxicity is often avoided as a side effect for rexinoid treatment. Several other potent RXR agonists, and their analogs, have been reported in the literature and rigorously evaluated (often in comparison to Bex) as potential cancer therapeutics with unique activity and side-effect profiles. Some of the more prominent examples include LGD100268, CD3254, and 9-cis-UAB30, to name only a few. Hence, the methods described herein are more widely applicable to a diverse array of RXR agonists. In terms of design, the structure-activity relationship (SAR) study is usually performed by modifying three distinct areas of the rexinoid base structure, either of the nonpolar or polar sides of the rexinoid and/or the linkage that joins them. For the synthesis of the modified base-structure analogs, often identical synthetic strategies used to access the base-structure are applied; however, reasonable alternative synthetic routes may need to be explored if the modified analog intermediates encounter bottlenecks where yields are negligible for a given step in the base-structure route. In fact, this particular problem was encountered and successfully resolved in our case study for generating an array of NEt-TMN analogs.

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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 first general method for the enantioselective construction of all-carbon quaternary centers on cyclopentanones by enantioselective palladium-catalyzed decarboxylative allylic alkylation is described. Employing the electronically modified (S)-(p-CF3)3-t-BuPHOX ligand, alpha-quaternary cyclopentanones were isolated in yields up to >99% with ee’s up to 94%. Additionally, in order to facilitate large-scale application of this method, a low catalyst loading protocol was employed, using as little as 0.15 mol % Pd, furnishing the product without any loss in ee.

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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 paper, we present a process concept for the atom economic hydroesterification of renewable methyl 10-undecenoate in thermomorphic multicomponent solvent (TMS) systems. Resulting dimethyl dodecanedioate is a polymer building block used e.g. in Nylon 6,12. As a suitable recycling technique a thermomorphic multicomponent solvent system consisting of methanol and dodecane is employed to recycle the palladium/1,2-bis(di-tert-butylphosphino)methyl)benzene/methanesulfonic acid catalyst. Product yields up to 79% and a high regioselectivtiy of 94% to the linear product are obtained. Low leaching of the catalyst into the product phase with 1% in respect of palladium and phosphorous is observed. Robustness and stability of the catalyst is shown in eight recycling runs without any loss of selectivity in the reaction.

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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 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 proportionality constant is the rate constant for the particular unimolecular reaction. the reaction rate is directly proportional to the concentration of the reactant. I hope my blog about 52409-22-0 is helpful to your research. Related Products of 52409-22-0

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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