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Synthesis, crystal structure, and conjugation properties of phenanthroline copper phosphine complexes

Facial synthetic method of 4,7-position conjugation extended phenanthrolines and X-ray structure of copper phosphine phenanthroline complexe were reported. The crystal structures showed pi-stacking and hydrogen bonding, and a small torsional angle between phen and phenylacetylene. These complexes exhibited strong conjugation dependant MLCT luminescence. The electronic and fluorescence spectra displayed a gradual red shift of the MLCT band as the conjugation increased. The presence of the phenyl groups reduced the energy of the pi? state in the d-pi? MLCT transition, allowing for the red shift. The electron-donating tri-isopropylsilyl (TIPS) groups on the ethynyl moiety increased the energy of the MLCT charge vector, allowing for the blue shift at the luminescence.

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

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NEW APPLICATION OF ORGANOBORON COMPOUNDS IN ORGANIC SYNTHESIS.

This paper describes the haloboration reaction of 1-alkynes and its application to organic synthesis. B-Bromo- or B-iodo-9-borabicyclo left bracket 3. 3. 1 right bracket -nonane (B-X-9-BBN) and other haloboranes react readily with 1-alkynes through Markovnikov cis-addition of the X-B moiety to C EQUVLNT C bonds. The haloboration occurs chemoselectively at terminal C EQUVLNT C bonds, but not at internal C EQUVLNT C, terminal and internal C equals C bonds. The haloboration adducts (I) thus obtained are valuable intermediates to afford various organic compounds stereospecifically in good yields, some of which are shown.

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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 1H-PYRAZOLOPYRIDINE DERIVATIVE AND PHARMACEUTICAL COMPOSITION COMPRISING THE SAME

The present invention relates to a novel 1H-pyrazolopyridine derivative and a pharmaceutical composition containing the same. The 1H-pyrazolopyridine derivative and the pharmaceutical composition containing the same can be usefully used for the prevention or treatment of autoimmune diseases or cancer.

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

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Selective dispersion of single-walled carbon nanotubes with specific chiral indices by poly(N-decyl-2,7-carbazole)

Physico-chemical methods to sort single-walled carbon nanotubes (SWNTs) by chiral index are presently lacking but are required for in-depth experimental analysis and also for potential future applications of specific species. Here we report the unexpected selectivity of poly-(N-decyl-2,7-carbazole) to almost exclusively disperse semiconducting SWNTs with differences of their chiral indices (n – m) ? 2 in toluene. The observed selectivity complements perfectly the dispersing features of the fluorene analogue poly(9,9-dialkyl-2,7- fluorene), which disperses semiconducting SWNTs with (n – m) ? 2 in toluene. The dispersed samples are further purified by density gradient centrifugation and analyzed by photoluminescence excitation spectroscopy. All-atom molecular modeling with decamer model compounds of the polymers and (10,2) and (7,6) SWNTs suggests differences in the pi-pi stacking interaction as origin of the selectivity. We observe energetically favored complexes between the (10,2) SWNT and the carbazole decamer and between the (7,6) SWNT and the fluorene decamer, respectively. These findings demonstrate that subtle structural changes of polymers lead to selective solvation of different families of carbon nanotubes. Furthermore, chemical screening of closely related polymers may pave the way toward simple, low-cost, and index-specific isolation of SWNTs.

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

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Highly regio- and stereoselective synthesis of multialkylated olefins through carbozirconation of alkynylboronates and sequential Negishi and Suzuki-Miyaura coupling reactions

Two Nobel couplings: The synthesis of tri- and tetraalkylated olefins has been achieved (see scheme). These multialkylated olefins were prepared by the zirconocene-mediated carbometalation of 1-alkynylboronates and subsequent sequential C-C bond formation with Negishi and Suzuki-Miyaura cross-coupling reactions using beta-hydrogen-containing alkylzinc reagents and alkyl electrophiles as coupling partners. Copyright

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

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1,2,6-SUBSTITUTED BENZIMIDAZOLES AS FLAP MODULATORS

The present invention relates to compounds of Formula (I), and solvates, hydrates, and pharmaceutically acceptable salts thereof, wherein X1, X1′, X1″, R1, R2 and R3 are as defined herein, useful as FLAP modulators. The invention also relates to pharmaceutical compositions comprising compounds of Formula (I). Methods of making and using the compounds of Formula (I) are also within the scope of the invention.

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

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Total synthesis of ent-dioxepandehydrothyrsiferol via a bromonium-initiated epoxide-opening cascade

(Chemical Equation Presented) In the first total synthesis of ent-dioxepandehydrothyrsiferol, the signature trans-anti-trans 7,7,6-fused tricyclic polyether framework was constructed in a single bromonium-initiated epoxide-opening cascade that incorporates both endo- and exo-selective epoxide openings, each directed by the substitution pattern of the epoxide (methyl groups). This study thus demonstrates the feasibility of a possible biogenesis.

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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 cytotoxicity and mechanism of action of new multinuclear Scaffold AuIII, PdII pincer complexes containing a bis(diphenylphosphino) ferrocene/non-ferrocene ligand

New multinuclear gold(iii), palladium(ii) pincer complexes containing bis(diphenylphosphino) ferrocene/non-ferrocene ligands of formula [(L)Au(mu2-eta2-CS3)Pd(dppf)](PF6)2, 1, and [(L)Au(mu2-eta2-CS3)Pd(dppe)](PF6)2, 2 (HL = 5-methoxy-1,3-bis (1-methyl-1H-benzo[d]imidazol-2-yl)benzene, dppf = 1,1?-bis(diphenylphosphino)ferrocene, and dppe = bis(diphenylphosphino)ethane) have been synthesized and fully characterized. Both complexes are more cytotoxic to a number of human cancer cell lines than cisplatin. Moreover, complex 1 is more active than auranofin as the reference gold compound against a panel of several human tumor cell lines. Chemosensitivity tests completed on cisplatin sensitive and resistant cell lines have confirmed that both complexes were able to overcome cisplatin resistance. The complexes successfully inhibited the enzymes thioredoxin reductase (TrxR) and glutathione reductase (GR). The cellular uptake of both gold and palladium of the complexes was studied, which indicated a high biological stability of the complexes. The complexes 1 and 2 increase the production of ROS in HCT-15 cells. In addition, these complexes induce major levels of cancer cell death by apoptosis.

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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 and structural studies on linear and macrocyclic Pd- and Pt-bridged butterfly Fe/S cluster complexes

Three types of (diphosphine)Pd- or Pt-bridged butterfly Fe/S cluster complexes have been prepared by a simple and convenient one-pot synthetic method. The first type of such complexes involves the linear (diphosphine)Pd- or Pt-bridged double-butterfly Fe/S clusters [(mu-RS)(mu-S=CS)Fe2(CO)6]2[M-(diphosphine)] (1-12; M = Pd and Pt; R = Et, t-Bu, Ph, and p-MeC6H4; diphosphine = dppe, dppv, and dppf), which were prepared by sequential reactions of monoanions [(mu-RS)(mu-CO)-Fe2(CO)6]- (formed in situ from Fe3(CO)12, RSH, and Et3N) with excess CS2, followed by treatment of the resulting monoanions [(mu-RS)(mu-S=CS)Fe2(CO)6]- with (diphosphine)MCl2. The second type of complexes involves the macrocyclic (diphosphine)M-bridged double-butterfly Fe/S clusters [mu-S(CH2)4S-mu][(mu-S=CS)-Fe2(CO)6]2[M(diphosphine)] (13-16; M = Pd and Pt; diphosphine = dppe and dppv), which were prepared by sequential reactions of dianion [{mu-S(CH2)4S-mu}{(mu-CO)Fe2(CO)6}2]2- (generated in situ from Fe3(CO)12, dithiol HS(CH2)4SH, and Et3N) with excess CS2, followed by treatment of the resultant dianion [{mu-S(CH2)4S-mu}{(mu-S=CS)Fe2(CO)6}2]2- with (diphosphine)MCl2. In contrast, when dithiol HS(CH2)4SH was replaced by HS(CH2)3SH (a dithiol with a shorter carbon chain), the aforementioned sequential reactions afforded the third type of macrocyclic complexes which involves the (diphosphine)M-bridged quadruple-butterfly Fe/S clusters [{mu-S(CH2)3S-mu}{(mu-S=CS)Fe2(CO)6}2]2[M(diphosphine)]2 (17-20; M = Pd and Pt; diphosphine = dppe and dppv). While the two possible pathways are suggested for production of the two types of novel macrocyclic Fe/S clusters 13-20, respectively, all new complexes 1-20 have been characterized by elemental analysis, spectroscopy, and, for some of them particularly, DFT calculations and X-ray crystallography.

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

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Conjugated polymers with large effective stokes shift: Benzobisdioxole- based poly(phenylene ethynylene)s

Phenyleneethynylene-based conjugated copolymers using benzo[1,2-d:4,5- d?]bis[1,3]dioxole (BDO) in the repeating unit are reported. The electronic structure of the BDO unit imparts a localized HOMO topology while the LUMO is delocalized over the polymer backbone, so that the lowest optical absorption band of the polymer has considerable intramolecular charge transfer character. This contrasts with published donor-acceptor polymers with localized LUMO and delocalized HOMO. The very large Stokes shifts of the monomers, which are due to the small oscillator strength of the lowest optical transition, are largely retained in the polymers as a result of covalently constrained dihedral angles in the substituents (not the backbone), as predicted/explained by calculations.

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