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From 1,2-difunctionalisation to cyanide-transfer cascades-Pd-catalysed cyanosulfenylation of internal (oligo)alkynes

Internal alkynes substituted by aliphatic or aromatic moieties or by heteroatoms were converted into sulphur-substituted acrylonitrile derivatives. Key is the use of Pd catalysis, which allows the addition of aromatic and aliphatic thiocyanates in an intra- A nd intermolecular manner. Substrates with several alkyne units underwent further carbopalladation steps after the initial thiopalladation step, thus generating in a cascade-like fashion an oligoene unit with sulphur at one terminus and the cyano group at the other.

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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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Scale-up chemical synthesis of thermally-activated delayed fluorescence emitters based on the dibenzothiophene-S,S-dioxide core

We report a procedure to linearly scale-up the synthesis of 2,8-bis(3,6-di-tert-butyl-9H-carbazol-9-yl)dibenzothiophene-S,S-dioxide (compound 4) and 2,8-bis(10H-phenothiazin-10-yl)dibenzothiophene-S,S-dioxide (compound 5) using Buchwald-Hartwig cross-coupling reaction conditions. In addition, we demonstrate a scaled-up synthesis of all non-commercially available starting materials that are required for the amination cross-coupling reaction. In the present article, we provide the detailed synthetic procedures for all of the described compounds, alongside their spectral characterization. This work shows the possibility to produce organic molecules for optoelectronic applications on a large scale, which facilitates their implementation into real world devices.

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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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Process for the carbonylation of ethylene and catalyst system for use therein

A catalyst system capable of catalyzing the carbonylation of ethylene and a process which uses such a system wherein the catalyst system is obtainable by combining a metal of Group VIII, e.g., palladium, or a compound thereof and a bidentate phosphine, e.g. bis(di-t-butyl phospino)-o-xylene, according to the equation C2H4¡ÀCO¡ÀROH?C2H5CO2R,.

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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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Arylsulfonamide ethers, and methods of use thereof

Novel arylsulfonamide ether compounds and pharmaceutical compositions thereof are described. The use of the novel arylsulfonamide ether compounds and pharmaceutical compositions thereof as inhibitors of interleukin-1beta converting enzyme and other cysteine proteases in the ICE family is also decribed. In addition, methods of treating stroke, inflammatory diseases, septic shock, repurfusion injury, Alzheimer’s disease, and shigellosis using a compound of the invention or a pharmaceutical composition thereof are described.

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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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Solution-processed white organic light-emitting diodes with blue fluorescent and orange-red thermally activated delayed fluorescent dendritic luminogens

In this work, dendritic luminogens, namely, 3ICz-Tr as a blue emitter and Tri-tNID as an orange-red emitter, were synthesized and used for the application of white organic light-emitting diodes (WOLEDs). These molecules have appropriately high molecular weights, which are favorable for the fabrication of thin films with fine surface morphologies. Interestingly, the blue emitting 3ICz-Tr displays fluorescent character and the orange-red emitting Tri-tNID exhibited thermally activated delayed fluorescence, which was confirmed by steady state and transient photoluminescence (TRPL) spectroscopy. Eventually, WOLED devices could be realized by mixing the two molecules and optimizing their mixture composition. Among the devices we fabricated, the device with Tri-tNID and 3ICz-Tr (0.5:99.5 wt ratio) without additional host material demonstrated nearly pure white emission, with the maximum EQE of 8.32% and CIE coordinate of (0.32, 0.30). Furthermore, by changing the composition of the two dendritic molecules, the emission color can be adjusted from a warm white to a cool white in the corresponding WOLED.

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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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Synthesis, Structure, and Coordination Chemistry of Phosphine-Functionalized Imidazole/Imidazolium Salts and Cleavage of a C-P Bond in an NHC-Phosphenium Salt using a Pd(0) Precursor

A simple method involving metal-halogen exchange reaction(s) to prepare various phosphine-functionalized imidazole/imidazolium salts and their coordination chemistry with different metal precursors has been described. Interestingly, the reaction of 1,3-dimethyl-2-(diphenylphosphino)-4-iodoimidazolium iodide (6) with Pd2(dba)3 in the presence of triphenylphosphine affords a Pd(II)-NHC complex which involves the cleavage of a C-P bond presumably occurring via oxidative addition of Pd(0) to a C-I bond to afford an in situ generated Pd(II) species, which subsequently reacts with another 1 equiv of 6 through the phosphine center to form an adduct followed by a dephosphinylation reaction. (Chemical Equation Presented).

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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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Regio- and Enantioselective Allylic Amination of Aliphatic MBH Adducts with N-Heteroaromatics

Palladium-catalyzed regio- and enantioselective allylic amination of aliphatic Morita-Baylis?Hillman (MBH) adducts with N-heteroaromatic nucleophiles (e.g., benzimidazole, 4,5-diphenylimidazole, benzotriazole, and purines) was achieved by using a spiroketal-based diphosphine (SKP) ligand, and afforded a range of chiral, branched N-allyl products with high selectivity.

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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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Molecular Engineering of Conjugated Polymers for Biocompatible Organic Nanoparticles with Highly Efficient Photoacoustic and Photothermal Performance in Cancer Theranostics

Conjugated polymer nanoparticles (CP NPs) are emerging candidates of “all-in-one” theranostic nanoplatforms with dual photoacoustic imaging (PA) and photothermal therapy (PTT) functions. So far, very limited molecular design guidelines have been developed for achieving CPs with highly efficient PA and PTT performance. Herein, by designing CP1, CP2, and CP3 using different electron acceptors (A) and a planar electron donor (D), we demonstrate how the D-A strength affects their absorption, emission, extinction coefficient, and ultimately PA and PTT performance. The resultant CP NPs have strong PA signals with high photothermal conversion efficiencies and excellent biocompatibility in vitro and in vivo. The CP3 NPs show a high PA signal to background ratio of 47 in U87 tumor-bearing mice, which is superior to other reported PA/PTT theranostic agents. A very small IC50 value of 0.88 mug/mL (CP3 NPs) was obtained for U87 glioma cell ablation under laser irradiation (808 nm, 0.8 W/cm2, 5 min). This study shows that CP NP based theranostic platforms are promising for future personalized nanomedicine.

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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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Synthesis of diketopyrrolopyrrole based conjugated polymers containing thieno[3,2-: B] thiophene flanking groups for high performance thin film transistors

New donor-acceptor (D-A) conjugate polymers based on 3,6-bis(2-bromothieno-[3,2-b]thiophen-5-yl)-2,5-bis(2-octyldodecyl)pyrrolo[3,4-c]-pyrrole-1,4-(2H,5H)-dione (Br-TTDPP) combined with three different electron-donating monomers bithiophene (BT), di(2-thienyl)ethene (TVT), and di(selenophene-2-yl)ethene (SVS) were synthesized. The optical band gap, electrochemical properties and organic field-effect transistor (OFET) device performance of the TTDPP-based polymers were systematically investigated. X-ray diffraction (XRD) was used to evaluate the molecular packing of the TTDPP-based polymers. Among three polymers, TTDPP-SVS showed the smallest d-spacing and the largest distance of 0.372 for pi-pi stacking. In particular, an OTFT having a TTDPP-SVS active layer showed the highest hole mobility of 0.196 cm2 V-1 s-1, the lowest threshold voltage down to -3.6 V, and the highest Ion/Ioff ratio of 6.5 ¡Á 104. This indicates that pi-extended SVS significantly improves charge transport properties.

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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 N-(Pyridin-4-yl)-1,5-naphthyridin-2-amines as Potential Tau Pathology PET Tracers for Alzheimer?s Disease

A mini-HTS on 4000 compounds selected using 2D fragment-based similarity and 3D pharmacophoric and shape similarity to known selective tau aggregate binders identified N-(6-methylpyridin-2-yl)quinolin-2-amine 10 as a novel potent binder to human AD aggregated tau with modest selectivity versus aggregated beta-amyloid (Abeta). Initial medicinal chemistry efforts identified key elements for potency and selectivity, as well as suitable positions for radiofluorination, leading to a first generation of fluoroalkyl-substituted quinoline tau binding ligands with suboptimal physicochemical properties. Further optimization toward a more optimal pharmacokinetic profile led to the discovery of 1,5-naphthyridine 75, a potent and selective tau aggregate binder with potential as a tau PET tracer.

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