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The first C(sp3)-C(sp2) cross-coupling of rare-earth metal alkyl complexes with aryl bromides has been developed. This reaction was conducted at low catalyst loading (0.5 mol%) and exhibited a broad substrate scope, thus providing a facile method for the synthesis of benzyltrimethylsilanes with diverse functional groups.

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

Can You Really Do Chemisty Experiments About Pd2(DBA)3

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A simple and regioselective synthesis of phenoxy esters and phenylthio esters is reported. The products are obtained by selective alkoxycarbonylation catalyzed by Pd2(dba)3, 1,4-bis(diphenylphisphino)butane (dppb), and syngas (CO/H2) in chloroform/alcohol. This methodology affords bifunctional products in good yield with excellent n-selectivity and without the need to use additives.

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

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Perovskite solar cells (PSCs) require both high efficiency and good long-term stability if they are to be commercialized. It is crucial to finely optimize the energy level matching between the perovskites and hole-transporting materials to achieve better performance. Here, we synthesize a fluorene-terminated hole-transporting material with a fine-tuned energy level and a high glass transition temperature to ensure highly efficient and thermally stable PSCs. We use this material to fabricate photovoltaic devices with 23.2% efficiency (under reverse scanning) with a steady-state efficiency of 22.85% for small-area (~0.094 cm2) cells and 21.7% efficiency (under reverse scanning) for large-area (~1 cm2) cells. We also achieve certified efficiencies of 22.6% (small-area cells, ~0.094 cm2) and 20.9% (large-area, ~1 cm2). The resultant device shows better thermal stability than the device with spiro-OMeTAD, maintaining almost 95% of its initial performance for more than 500 h after thermal annealing at 60 C.

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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 invention relates to provide a following formula (III) shows the fragrant alkyne base by the substituted heterocyclic ketone compounds, said method comprising: in under the nitrogen atmosphere, the reaction kettle point pen in the (I) compounds, of formula (II) compound and organic solvent, heating to 60 – 80 C stirring and mixing 10 – 20 minutes, then adding the compound catalyst, organic ligands and compounding chemicals, and thermal insulation to continue stirring reaction 8 – 12 hours, after the reaction is finished after treatment states the type (III) compound, Wherein R is H, C1 – C6 Alkyl, C1 – C6 Alkoxy or halogen. The method through the composite catalyst, organic ligand, compounding chemicals and organic solvent synergistic effect, thus effectively increases the yield of the product, to obtain the extremely excellent technical effects, demonstrate a wide range of industrial application prospect and production potential. (by machine translation)

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

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Chlorophyll(Chl)-a derivatives containing some rigid linkers in the C3-substituent, inserted between a hydroxymethyl group and a zinc 131-oxo-chlorin moiety, were synthesized as models of bacteriochlorophyll-c/d/e molecules in the main light-harvesting antennae (chlorosomes) of photosynthetic green bacteria. These model compounds were synthesized from a C3-ethynylated Chl-a derivative via several coupling reactions, and the lengths of the linkers were controlled by ethynylene and p-phenylene groups. In less polar organic solvents or an aqueous micellar solution, some derivatives self-aggregated in a J-type fashion similar to that observed in natural chlorosomes, which was confirmed with UV/Vis absorption and CD spectroscopies. Their self-aggregation abilities were dependent on the length of the inserted linkers and the conformation of the propargylic/benzylic alcoholic hydroxy 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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We carried out a comprehensive study on the generality, scope, limitations, and mechanism of the palladium-catalyzed hydrophosphorylation of alkynes with P(O)-H compounds (i.e., H-phosphonates, H-phosphinates, secondary phosphine oxides, and hypophosphinic acid). For H-phosphonates, Pd/dppp was the best catalyst. Both aromatic and aliphatic alkynes, with a variety of functional groups, were applicable to produce the Markovnikov adducts in high yields with high regioselectivity. Aromatic alkynes showed higher reactivity than aliphatic alkynes. Terminal alkynes reacted faster than internal alkynes. Sterically crowded H-phosphonates disfavored the addition. For H-phosphinates and secondary phosphine oxides, Pd/dppe/Ph2P(O)OH was the catalyst of choice, which led to highly regioselective formation of the Markovnikov adducts. By using Pd(PPh3)4 as the catalyst, hypophosphinic acid added to terminal alkynes to give the corresponding Markovnikov adducts. Phosphinic acids, phosphonic acid, and its monoester were not applicable to this palladium-catalyzed hydrophosphorylation. Mechanistic studies showed that, with a terminal alkyne, (RO)2P(O)H reacted, like a Br°nsted acid, to selectively generate the alpha-alkenylpalladium intermediate via hydropalladation. On the other hand, Ph(RO)P(O)H and Ph2P(O)H gave a mixture of alpha- and beta-alkenylpalladium complexes. In the presence of Ph2P(O)OH, hydropalladation with this acid took place first to selectively generate the alpha-alkenylpalladium intermediate. A subsequent ligand exchange with a P(O)H compound gave the phosphorylpalladium intermediate which produced the Markovnikov adduct via reductive elimination. Related intermediates in the catalytic cycle were isolated and characterized.

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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 homogeneous catalysis, the catalyst is in the same phase as the reactant. The number of collisions between reactants and catalyst is at a maximum.In a patent, 52409-22-0, name is Pd2(DBA)3, introducing its new discovery. category: catalyst-palladium

A thermally stable 2,2-difluorovinylzinc-TMEDA complex was prepared via a deprotonation-transmetallation sequence starting from commercially available 1,1-difluoroethylene. The complex thus formed was successfully applied to transition metal-catalyzed cross-coupling reactions with a wide range of organic halides, which led to the syntheses of 2,2-difluorovinyl compounds. On treatment with the difluorovinylzinc-TMEDA complex in the presence of an appropriate palladium or copper catalyst, alkenyl, alkynyl, allyl, and benzyl halides effectively underwent difluorovinylation to afford 1,1-difluoro-1,3-dienes, 1,1-difluoro-1,3-enynes, 1,1-difluoro-1,4-dienes, and (3,3-difluoroallyl)arenes, respectively.

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

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Introduction: Imidazoline receptors (IRs) have been established as distinct receptors, and have been categorized into at least two subtypes (I1R and I2R). I2Rs are associated with depression, Alzheimer’s disease, Huntington’s disease and Parkinson’s disease. A few positron emission tomography (PET) probes for I2Rs have been synthesized, but a selective PET probe has not been evaluated for the imaging of I2Rs by PET. We labeled a selective I2R ligand 2-(3-fluoro-4-tolyl)-4,5-dihydro-1H-imidazole (FTIMD) with 11C and performed the first imaging of I2Rs by PET using 2-(3-fluoro-[4-11C]tolyl)-4,5-dihydro-1H-imidazole ([11C]FTIMD). Methods: [11C]FTIMD was prepared by a palladium-promoted cross-coupling reaction of the tributylstannyl precursor and [11C]methyl iodide in the presence of tris(dibenzylideneacetone)dipalladium(0) and tri(o-tol)phosphine. Biodistribution was investigated in rats by tissue dissection. [11C]FTIMD metabolites were measured in brain tissues and plasma. Dynamic PET scans were acquired in rats, and the kinetic parameters estimated. Results: [11C]FTIMD was successfully synthesized with a suitable radioactivity for the injection. Co-injection with 0.1 mg/kg of cold FTIMD and BU224 induced a significant reduction in the brain-to-blood ratio 15 and 30 min after the injection. In metabolite analysis, unchanged [11C]FTIMD in the brain was high (98%) 30 min after the injection. In PET studies, high radioactivity levels were observed in regions with a high density of I2R. The radioactivity levels and VT values in the brain regions were prominently reduced by 1.0 mg/kg of BU224 pretreatment as compared with control. Conclusion: [11C]FTIMD showed specific binding to I2Rs in rat brains with a high density of I2R.

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

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Mitochondria are recognized as one of the most important targets for new drug design in cancer, cardiovascular, and neurological diseases. Currently, the most effective way to deliver drugs specifically to mitochondria is by covalent linking a lipophilic cation such as an alkyltriphenylphosphonium moiety to a pharmacophore of interest. Other delocalized lipophilic cations, such as rhodamine, natural and synthetic mitochondria-targeting peptides, and nanoparticle vehicles, have also been used for mitochondrial delivery of small molecules. Depending on the approach used, and the cell and mitochondrial membrane potentials, more than 1000-fold higher mitochondrial concentration can be achieved. Mitochondrial targeting has been developed to study mitochondrial physiology and dysfunction and the interaction between mitochondria and other subcellular organelles and for treatment of a variety of diseases such as neurodegeneration and cancer. In this Review, we discuss efforts to target small-molecule compounds to mitochondria for probing mitochondria function, as diagnostic tools and potential therapeutics. We describe the physicochemical basis for mitochondrial accumulation of lipophilic cations, synthetic chemistry strategies to target compounds to mitochondria, mitochondrial probes, and sensors, and examples of mitochondrial targeting of bioactive compounds. Finally, we review published attempts to apply mitochondria-targeted agents for the treatment of cancer and neurodegenerative diseases.

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

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Palladium-catalyzed allylic C?H oxidation has been widely studied, but most precedents use acetic acid as the coupling partner. In this study, a method compatible with diverse carboxylic acid partners has been developed. Use of a Pd0 precatalyst under aerobic reaction conditions leads to oxidation of Pd0 by O2 in the presence of the desired carboxylic acid to generate a PdII dicarboxylate that promotes acyloxylation of the allylic C?H bond. Good-to-excellent yields are obtained with a roughly 1:1 ratio of the alkene and carboxylic acid reagents. Optimized reaction conditions employ 4,5-diazafluoren-9-one (DAF) as a ligand, in combination with a quinone/iron phthalocyanine cocatalyst system to support aerobic catalytic turnover.

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