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Provided are PDE1 inhibitors of Formula I, processes for their production, their use as pharmaceuticals, and pharmaceutical compositions comprising them

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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 palladium-catalyzed ligand controlled regioselective A-coupling reaction of secondary propargyl carbonates and ethyl 2-(pyridin-2-yl)acetate derivatives has been described, leading to C-3 benzyla-ated indolizines for the first time in moderate to good yields. DBFphos as the ligand is crucial to this high regioselective annulation reaction, and a plausible reaction mechanism has been proposed.

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

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Synthetic access to the zerovalent palladium complexes {[(o-Ph2PC6H4)2BPh]Pd(L)} (L = pyridine (8a), 2,6-lutidine (8b)) is reported. Structural characterization and DFT analysis of 8a revealed a strong Pd?B interaction, which appears to inhibit oxidative addition reactions. Activation of allyl acetate is possible by reversible transfer of the acetate leaving group to the ligand’s borane functionality. Catalytic activity in the allylic substitution of allyl acetate with HNEt2 is sensitive to the presence of free acetate, which reduces borane inhibition by reversible borate formation.

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

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Novel phosphorescent metal complexes containing 2-phenylquinoline ligands with at least two substituents on the quinoline ring are provided. The disclosed compounds have low sublimation temperatures that allow for ease of purification and fabrication into a variety of OLED devices.

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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 material with diverse self-assembled morphologies is extremely important and highly desirable because such samples can provide tunable optical and electronic properties, which are critical in applications such as organic photovoltaics, microelectronics and bio-imaging. Moreover, the synthesis and controllable self-assembly of H-shaped bichromophoric perylenediimides (PDIs) are needed to advance these materials in organic photovoltaics, microelectronics and bio-imaging; however, this has remained a great challenge thus far. Here, we successfully synthesize a novel H-shaped bichromophoric PDI Gemini through the palladium-catalyzed coupling reaction. The as-prepared PDI Gemini exhibited unprecedented tunable self-assembly behavior in solution, yielding diverse low-dimensional superstructures, such as one-dimensional (1D) helices, two-dimensional (2D) rectangular nanocrystals, pyramid-shaped parallelograms, ultralarge micro-sheets, and uniform nanospheres, under different self-assembly conditions. Of particular interest, the 2D hierarchical superstructures along with their formation mechanisms represent the first finding in the self-assembly of PDI-based molecules. This study opens a new avenue for tunable self-assembly of conjugated molecules and affords opportunities for the fabrication of novel self-assembled optical and electronic materials based on PDI molecules.

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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 efficient and versatile Pd-catalyzed tandem C-N bond formation between aryl halides and primary amines is developed. The transformation allows a one-pot synthesis of phenoxazine and phenothiazine derivatives with a broad range of substitution patterns from readily available precursors.

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

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Disclosed are compounds of Formula 1, or pharmaceutically acceptable salts thereof, wherein R1, R2, R3, and R4 are defined in the specification. This disclosure also relates to materials and methods for preparing compounds of Formula 1, to pharmaceutical compositions which contain them, and to their use for treating Type I hypersensitivity reactions, autoimmune diseases, inflammatory disorders, cancer, non-malignant proliferative disorders, and other conditions associated with BTK.

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

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To investigate the effect of the fluoride phenyl side-chains into quinoxaline (PQx) unit on the photovoltaic performances of polymers, we demonstrated the synthesis and characterization of two novel wide-bandgap (WBG) copolymers, PIDT-DTPQx and PIDT-DTFPQx, in which indacenodithiophene (IDT), 2,3-diphenylquinoxaline (PQx) (and/or 2,3-bis(4-fluorophenyl)quinoxaline (FPQx)) and thiophene (T) were used as the donor (D) unit, acceptor (A) unit and pi-bridge, respectively. Compared to the non-fluorine substituted PIDT-DTPQx, fluorine substituted PIDT-DTFPQx presents a deep HOMO energy level and a high hole mobility. Obviously, improved the Voc, Jsc, and FF simultaneously, giving rise to overall efficiencies in the PIDT-DTFPQx/PC71BM-based PSCs. A highest PCE of 5.78% was obtained with a Voc of 0.86 V, Jsc of 10.84 mA cm-2 and FF of 61.7% in the PIDT-DTFPQx/PC71BM-based PSCs, while PIDT-DTPQx based devices also demonstrated a PCE of 5.11%, under the illumination of AM 1.5G (100 mW cm-2). Note that these PCE values were achieved for PSCs without any extra treatments. Furthermore, these optimal devices have a film thickness of about 175 nm for the polymer/PC71BM-based active layers. The results provide that introduction of the fluorine atom into quinoxaline unit by side-chain engineering is one of the effective strategies to construct the promising polymer donor materials for future application of large-area polymer solar cells.

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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 novel strategy for direct aryl hydroxylation via Pd-catalysed Csp2-H activation through an unprecedented hydroxyl radical transfer from 1,4-dioxane, used as a solvent, is reported with bio relevant and sterically hindered heterocycles and various acyclic functionalities as versatile directing 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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Building on our previous discovery and reactivity explorations of the Pd(I) dimer [(PtBu3)PdBr]2-mediated halogen exchange of aryl iodides [ Chem. Sci. 2013, 4, 4434 ], this report presents kinetic studies of this process, giving first-order kinetic dependence in the Pd(I) dimer and aryl iodide. An activation free energy barrier of DeltaG? = 24.9 ± 3.3 kcal/mol was experimentally determined. Extensive computational studies on the likely reaction pathway were subsequently carried out. A variety of DFT methods were assessed, ranging from dispersion-free methods to those that better account for dispersion (M06L, omegaB97XD, D3-DFT). While significant discrepancies in the quantitative prediction of activation barriers were observed, all computational methods consistently predicted the analogous qualitative reactivity that is in agreement with all spectroscopic and reactivity data collected. Overall, these data provide compelling additional support of the direct reactivity of Pd(I)-Pd(I) with aryl iodides.

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