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Catalytic enantioconvergent decarboxylative allylic alkylation of allyl indolenin-3-carboxylates

A catalytic enantioconvergent process has been developed for the conversion of racemic allyl indolenin-3-carboxylates into enantiomerically enriched C3-quaternary indolenines. A Pd-catalyzed decarboxylative allylic alkylation reaction was employed for both stereoablation of the racemic allyl indolenin-3-carboxylates and enantioselective formation of the quaternary carbon center. The enantioconvergent conversion of racemic allyl indolenin-3- carboxylates into enantiomerically enriched C3-quaternary indolenines is reported. A Pd-catalyzed decarboxylative allylic alkylation reaction is employed for both stereoablation and enantioselective formation of the quaternary carbon center. Copyright

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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, optoelectronic properties and photovoltaic performances of wide band-gap copolymers based on dibenzosilole and quinoxaline units, rivals to P3HT

Three pi-conjugated alternating copolymers, based on dibenzosilole as an electron-rich unit and fluorinated or non-fluorinated quinoxaline as an electron-withdrawing unit, connected through thiazole or thiophene moieties, have been synthesized, fully characterized and applied as donors in polymer solar cells (PSCs). The three copolymers, namely PDBS-TQx, PDBS-TQxF and PDBS-TzQx, belong to the wide band-gap semiconductor materials family, and they show an absorption edge in the visible region close to 650 nm. In order to tune the position of the polymer energy levels, and in particular to decrease their HOMO energy level, we compare the use of a thiazole spacer sandwiching the electron-deficient moiety as an alternative way to the popular backbone fluorination. PSCs based on a blend of PDBS-TQx and [6,6]-phenyl-C71-butyric acid methylester (PC71BM) as an active layer have shown the best device performances with a maximum power conversion efficiency (PCE) of 5.14% for the active area of 0.28 cm2 (under standard illumination of AM 1.5G, 1000 W m-2). Interestingly this polymer outperforms P3HT:(PC61BM) solar cells used as a reference material in this work. In addition to the thorough characterization data, including among other spectroscopy techniques, XRD, OFET, AFM and nc-AFM, we discuss in detail the relationship between the chemical structures of the three polymers, their optoelectronic properties, the phase separation in blends with PC71BM and their photovoltaic performances.

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

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Investigation of photochromic fluorescence features and synthesis of diarylethene type naphthalimide compounds

The aim of the study was to synthesise novel photo-exchangeable photochromic fluorescent compounds. 3,4-Bis(3,5-dimethyl-4-pyrazolyl)-N-butyl-1,8-naphthalimide 6 and 3,4-bis (1,3,5-trimethyl-4-pyrazolyl)-N-butyl-1,8-naphthalimide 7 naphthalimide derivative new compounds were prepared via two-step Suzuki coupling reaction of pyrazolylboronic acid esters from N-butyl-4-bromo-3-iodo-1,8-naphthalimide and characterized by1H-NMR,13C-NMR, MS and FTIR. Their photochromic fluorescence properties were investigated. Additionally, a solvent effect on the fluorescent properties of 6 and 7 was investigated. Increase of organic solvent polarity results in a red shift (to longer wavelengths) of the fluorescence emissions.

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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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Novel wide-bandgap copolymer bearing alkylthio-thiophene-substituted benzodithiophene and methyl thiophene-3-carboxylate for highly stable fullerene-free simple polymer solar cells

We successfully synthesized a wide-bandgap p-type copolymer, 3MT-Th-S, bearing alkylthio-substituted benzodithiophene (BDT) as a donor and methyl-3-thiophenecarboxylate (3MT) as a weak electron acceptor. The electron affinity of the sulfur atom in the 2-ethylhexylthio side chains tethered to the thiophene units induces a low-lying highest occupied molecular orbital (HOMO) energy level in the corresponding polymer. 3MT-Th-S displays a strong absorption band from 400 to 600 nm, resulting in a relatively wide optical bandgap. Thin films of 3MT-Th-S exhibit a prominent face-on orientation in the out-of-plane profile, which might be a favorable orientation for moving charge carriers in the vertical direction in polymer solar cells (PSCs). Non-fullerene PSCs based on 3MT-Th-S as the donor and an n-type small molecule (ITIC, ITIC-Me, or IMIDT) were fabricated, and their performance was investigated in detail. Among the PSC devices bearing three different acceptors, the 3MT-Th-S:ITIC-based PSC exhibits the highest power conversion efficiency of 7.86% with a high short-circuit current density of 16.11 mA cm?2 and an open circuit voltage of 0.96 V. The high PCE values of PSC using the as-cast blend films of 3MT-Th-S and ITIC as an active layer without solvent additive are attributed to the low-lying HOMO level of the donor polymer, the complementary absorption behavior of the blend film, the face-on arrangement of polymer chains on the substrate, and the well-formed morphology of the binary blend film. These results clearly demonstrate that 3MT-Th-S is a promising wide-bandgap p-type polymer for high-performance fullerene-free simple PSCs.

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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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Inhibitors of c-Jun N terminal kinases (JNK) and other protein kinases

The present invention provides compounds of formula I: 1where R1 is H, CONH2, T(n)?R, or T(n)?Ar2, n may be zero or one, and G, XYZ, and Q are as described below. These compounds are inhibitors of protein kinase, particularly inhibitors of JNK, a mammalian protein kinase involved cell proliferation, cell death and response to extracellular stimuli. The invention also relates to methods for producing these inhibitors. The invention also provides pharmaceutical compositions comprising the inhibitors of the invention and methods of utilizing those compositions in the treatment and prevention of various disorders.

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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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Bis-cyclooctatetraene tripalladium sandwich complexes

We report synthesis and structural characterization of bis- cyclooctatetraene trinuclear palladium sandwich complexes. The non-planar cyclooctatetraene ligands flank an isosceles Pd3 triangle, which is supported by one equatorial ligand. The Royal Society of Chemistry.

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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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Redox-neutral photocatalytic strategy for selective C?C bond cleavage of lignin and lignin models via PCET process

It remains challenging to achieve the selective cleavage of C?C bonds in lignin or lignin model compounds to produce aromatic products in high yield and selectivity. We have developed a redox-neutral photocatalytic strategy to accomplish this goal in both beta-O-4 and beta-1 lignin models at room temperature (RT) via proton-coupled electron transfer (PCET) process without any pretreatments of substrate, by adjusting the alkalinity of base to obtain a lignin models/base PCET pair with a bond dissociation free energy close to 102 kcal/mol. Without breaking down Cbeta?Cgamma bond and any C?O bonds, this PCET method is 100% atom economy and produces exclusive Calpha?Cbeta bond cleavage products, such as benzaldehydes (up to 97%) and phenyl ethers (up to 96%), in high to excellent yields and selectivities. Preliminary studies indicated that the PCET strategy is also effective for the depolymerization of native lignin at RT, thus providing significantly important foundation to the depolymerization of lignin.

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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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Extended Ladder-Type Benzo[k]tetraphene-Derived Oligomers

Well-defined, fused-ring aromatic oligomers represent promising candidates for the fundamental understanding and application of advanced carbon-rich materials, though bottom-up synthesis and structure?property correlation of these compounds remain challenging. In this work, an efficient synthetic route was employed to construct extended benzo[k]tetraphene-derived oligomers with up to 13 fused rings. The molecular and electronic structures of these compounds were clearly elucidated. Precise correlation of molecular sizes and crystallization dynamics was established, thus demonstrating the pivotal balance between intermolecular interaction and molecular mobility for optimized processing of highly ordered solids of these extended conjugated molecules.

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

The important role of Pd2(DBA)3

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Real-time analysis of Pd2(dba)3 activation by phosphine ligands

A combination of UV-Vis spectroscopy and electrospray ionization mass spectrometry is used for real-time monitoring of Pd2(dba)3 activation with sulfonated versions of PPh3 and Buchwald-type ligands. This provides insight into the effect of ligand and preparation conditions on activation and allows for establishment of rational activation protocols.

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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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Mechanistic Study of the Role of Substrate Steric Effects and Aniline Inhibition on the Bis(trineopentylphosphine)palladium(0)-Catalyzed Arylation of Aniline Derivatives

The mechanism of the bis(trineopentylphosphine)palladium(0) (Pd(PNp3)2)-catalyzed coupling of aryl halides and aniline derivatives was studied in an effort to understand the role of substrate steric effects on the reaction. Prior studies had shown that the rate of Pd/PNp3-catalyzed coupling of aryl bromides and aniline derivatives was largely unaffected by substrate steric demand. The oxidative addition of aryl bromides to Pd(PNp3)2 is found to follow first-order kinetics with a rate that is independent of both ligand and aryl halide concentration. Thus, the rate limiting step for oxidative addition of aryl bromides is irreversible ligand dissociation. In the case of aryl chlorides, the oxidative addition rate has a first-order dependence on [ArCl] and an inverse dependence on [PNp3], indicating a mechanism involving reversible dissociation of the ligand followed by rate limiting oxidative addition. This difference in aryl halide effect was also found for the catalytic coupling reaction. Aryl bromide steric demand does not affect the coupling rate with hindered anilines, whereas the coupling rate of aryl chlorides is negatively affected by substrate steric demand. These results suggest that oxidative addition is rate limiting in the catalytic reaction for aryl chlorides but that oxidative addition is not rate limiting for aryl bromides. Aniline was found to give coupling rates significantly slower than those of 2,6-diisopropylaniline for both aryl bromides and chlorides. Aniline promotes the decomposition of the [(PNp3)Pd(Ar)(mu-X)]2 catalytic intermediate to a catalytically inactive palladacycle ([(kappa2-P,C-Np2PCH2C(Me2)CH2)Pd(mu-X)]2) through C-H activation of a neopentyl group and elimination of arene. These studies show that the ability of the Pd/PNp3 catalyst system to tolerate steric demand in aryl bromides stems from the fact that the rate limiting step of the catalytic cycle is independent of the concentration and steric demand of aryl bromides. A catalyst deactivation pathway involving ligand metalation was identified that is promoted by unhindered aniline derivatives.

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