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N-Type pyromellitic diimide-benzodithiophene-containing conjugated polymers for all-polymer solar cells with high open-circuit voltage

n-Type conjugated polymers based on pyromellitic diimide units are synthesized.Electrochemical results illustrate that both polymers have LUMO levels at -3.5 to -3.6 eV.All-polymer solar cells based on the prepared polymers are fabricated.The PSC based on the blend of P3HT and P2 shows a high Vocof 0.96 V.n-Type conjugated polymers were synthesized by using pyromellitic diimide monomers with two different alkyl side chain substitutions as electron-accepting units and benzodithiophene as electron-donating unit via Stille coupling reaction. The obtained polymers were characterized by UV-vis spectroscopy and cyclic voltammetry. The results illustrate that the substituted alkyl side chains 2-ethylhexyl and 2-octyldodecyl have negligible effect on the optical properties of the resulting polymers. The LUMO levels of the polymers located at -3.5 to -3.6 eV. All-polymer bulk heterojunction solar cell with “P3HT” as p-type polymer in standard architecture were fabricated, the cell based on the polymer with 2-octyldodecyl side chain (P2) shows good photovoltaic performance with power conversion efficiency up to 0.47% and a high open circuit voltage of 0.96 V.

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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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An Exclusively trans-Selective Chlorocarbamoylation of Alkynes Enabled by a Palladium/Phosphaadamantane Catalyst

Pharmaceutically relevant methylene oxindoles are synthesized by a palladium(0)-catalyzed intramolecular chlorocarbamoylation reaction of alkynes. A relatively underexplored class of caged phosphine ligands is uniquely suited for this transformation, enabling high levels of reactivity and exquisite trans selectivity. This report entails the first transition-metal-catalyzed atom-economic addition of a carbamoyl chloride across an alkyne.

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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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Microwave-Assisted Domino Heck Cyclization and Phosphorylation: Synthesis of Phosphorus Containing Heterocycles

A domino [Pd]-catalyzed intramolecular Heck cyclization followed by intermolecular phosphorylation, for the construction of phosphorus containing heterocyclic compounds, is presented. Notably, the process is accelerated by microwave heating conditions and enabled the construction of C?C and C?P bonds in short reaction times.

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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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Kinase inhibitors as potential agents in the treatment of multiple myeloma

Recent years have witnessed a dramatic increase in the number of therapeutic options available for the treatment of multiple myeloma (MM) – from immunomodulating agents to proteasome inhibitors to histone deacetylase (HDAC) inhibitors and, most recently, monoclonal antibodies. Used in conjunction with autologous hematopoietic stem cell transplantation, these modalities have nearly doubled the disease’s five-year survival rate over the last three decades to about 50%. In spite of these advances, MM still is considered incurable as resistance and relapse are common. While small molecule protein kinase inhibitors have made inroads in the therapy of a number of cancers, to date their application to MM has been less than successful. Focusing on MM, this review examines the roles played by a number of kinases in driving the malignant state and the rationale for target development in the design of a number of kinase inhibitors that have demonstrated anti-myeloma activity in both in vitro and in vivo xenograph models, as well as those that have entered clinical trials. Among the targets and their inhibitors examined are receptor and non-receptor tyrosine kinases, cell cycle control kinases, the PI3K/AKT/mTOR pathway kinases, protein kinase C, mitogen-activated protein kinase, glycogen synthase kinase, casein kinase, integrin-linked kinase, sphingosine kinase, and kinases involved in the unfolded protein response.

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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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Pd-Catalyzed alpha-Arylation of Sulfones in a Three-Component Synthesis of 3-[2-(Phenyl/methylsulfonyl)ethyl]indoles

A novel four-step domino process for the synthesis of 3-[2-(aryl/alkylsulfonyl)ethyl]indoles starting from readily available 2-iodoanilines is reported. The domino reaction is based on the intramolecular palladium-catalyzed alpha-arylation of sulfones, which was combined with both intermolecular aza-Michael and Michael addition reactions using vinyl sulfones as the electrophile. The domino process produced good yields and tolerated the presence of substituents with different electronic properties on the aniline ring. In addition, density functional theory (DFT) calculations were carried out to gain more insight into the formation of the observed indole derivatives.

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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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Pyrazolo-pyridine derivatives as ligands for GABA receptors

Pyrazolo[4,3-c]pyridin-3-one derivatives substituted at the 2-position by an optionally substituted aryl or heteroaryl moiety, and having pendant substituents at the 7-position and optionally also at the 6-position, are selective ligands for GABA A receptors, particularly having high affinity for the alpha2 and/or alpha3 subunit, and are useful in the treatment and/or prevention of disorders of the central nervous system, including anxiety and convulsions.

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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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Modular Dual-Tasked C-H Methylation via the Catellani Strategy

We report a dual-tasked methylation that is based on cooperative palladium/norbornene catalysis. Readily available (hetero)aryl halides (39 iodides and 4 bromides) and inexpensive MeOTs or trimethylphosphate are utilized as the substrates and methylating reagent, respectively. Six types of “ipso” terminations can modularly couple with this “ortho” C-H methylation to constitute a versatile methylation toolbox for preparing diversified methylated arenes. This toolbox features inexpensive methyl sources, excellent functional-group tolerance, simple reaction procedures, and scalability. Importantly, it can be uneventfully extended to isotope-labeled methylation by switching to the corresponding reagents CD3OTs or 13CH3OTs. Moreover, this toolbox can be applied to late-stage modification of biorelevant substrates with complete stereoretention. We believe these salient and practical features of our dual-tasked methylation toolbox will be welcomed by academic and industrial researchers.

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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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Differential Dihydrofunctionalization of Terminal Alkynes: Synthesis of Benzylic Alkyl Boronates through Reductive Three-Component Coupling

The differential dihydrofunctionalization of terminal alkynes is accomplished through the reductive three-component coupling of terminal alkynes, aryl halides, and pinacolborane. The transformation results in hydrofunctionalization of both pi-bonds of an alkyne in a single reaction promoted by cooperative action of a copper/palladium catalyst system. The differential dihydrofunctionalization reaction has excellent substrate scope and can be accomplished in the presence of esters, nitriles, alkyl halides, epoxides, acetals, alkenes, aryl halides, and silyl ethers. Mechanistic experiments indicate that the reaction proceeds through copper-catalyzed hydroboration followed by a second hydrocupration. The resulting heterobimetallic complex is the key intermediate that participates in the subsequent palladium-catalyzed cross-coupling, which furnishes benzylic alkyl boronate products.

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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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Enantioselective and alpha-regioselective allylic amination of Morita-Baylis-Hillman acetates with simple aromatic amines catalyzed by planarly chiral ligand/palladium catalyst

An asymmetric allylic amination of Morita-Baylis-Hillman acetates with simple aromatic amines catalyzed by planarly chiral ligand/palladium-catalyst was developed in good yield with excellent alpha-regioselectivity (alpha/gamma up to 30:1) and moderate enantioselectivity (up to 70% ee).

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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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Palladium-Catalyzed seven-membered silacycle construction: 1,7-enyne hydroxycyclization to give a benzosilepine skeleton

A palladium-catalyzed hydroxycyclization reaction of 1,7-enynes to afford seven-membered silacycles (1H-benzo[b]silepine skeletons) is developed. This is the first example of both seven-membered ring construction from enynes using a palladium catalyst and hydroxycyclization of enynes to give seven-membered silacycles.

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