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A method for the catalytic alpha-arylation of indolin-3-ones was developed. The catalytic system comprising Pd(dba)2 and PAd3 was found to be optimal for the transformation. The protocol features broad functional group compatibility in that a range of arylated indoxyl derivatives bearing a fully substituted carbon center was synthesized with high efficiency. A preliminary bioassay study revealed that the selected indole-substituted indolin-3-ones exhibit favorable cytotoxic activities against HCT-116 cancer cell line.

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

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Both symmetrical and unsymmetrical cyclophanes containing disilane units, tetrasila[2.2]cyclophanes 1-9, were synthesized. The syn and anti conformations and the kinetics of inversion between two anti-isomers were investigated by X-ray diffraction and variableerature NMR analysis, respectively. The flipping motion of two aromatic rings was affected by the bulkiness of the aromatic moiety (1 vs 6), the phase (solid vs solution), and the inclusion by host molecules (1 vs 1?[Ag2L]2+). The photophysical, electrochemical, and structural properties of the compounds were thoroughly investigated. Unsymmetrical tetrasila[2.2]cyclophanes 5-8 displayed blue-green emission arising from intramolecular charge transfer. Compound 6 emitted a brilliant green light in the solid state under 365 nm irradiation and showed a higher fluorescence quantum yield in the solid state (phi = 0.49) than in solution (phi = 0.05). We also obtained planar chiral tetrasila[2.2]cyclophane 9, which showed interesting chiroptical properties, such as a circularly polarized luminescence (CPL) with a dissymmetry factor of |glum| = ca. 2 × 10-3 at 500 nm. Moreover, an organic green light-emitting diode that showed a maximum external quantum efficiency (next) of ca. 0.4% was fabricated by doping 4,4?-bis(2,2?-diphenylvinyl)-1,1?-biphenyl with 6.

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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 new rhenium-tin complex Re2(CO)8(mu-SnPh2)2, 1 was obtained in 52% yield from the reaction of Re2(CO)8(mu-H)[mu-C(H)C(H)Bu] with Ph3SnH. Compound 1 contains two SnPh2 groups bridging a long Re-Re single bond, Re-Re = 3.1971(4) A [3.1902(4) A], Re-Sn = 2.7429(4) A [2.7445(4) A], and 2.7675(4) [2.7682(5) A]. A bis-Pd(PBut3) adduct of 1, Pd2Re2(CO)8(mu-SnPh2)2(PBut3)2, 2 was obtained from the reaction of 1 with Pd(PBut3)2. Compound 2 contains Pd(PBut3) groups bridging two of its four Re-Sn bonds. The Re-Re bond and the unbridged Re-Sn bonds in 2 are significantly longer than those in 1, 3.245(1) A and 2.8167(14) A, respectively. Fenske-Hall molecular orbital calculations on 1 and 2 have been performed to explain the metal-metal bonding in these unusual mixed-metal polynuclear metal complexes. 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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The rate of palladium catalysed phenylation of allylic alcohols is markedly enhanced by addition of tertiary amines, presumably by co-ordination to the palladium atom to form very reactive species.

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

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An in-depth mechanistic study on the palladium-catalyzed direct arylation of imidazoles at the C-5 position is presented. The interactions of triphenylphosphine (PPh3)-ligated aryl-Pd species with 1,2-dimethyl-1H-imidazole (dmim) have been studied in detail. In contrast with previous suggestions, phosphine-ligated organo-Pd species are not active and the reaction proceeds through imidazole-ligated organo-Pd intermediates. The kinetics of the oxidative addition of aryl halides with dmim-ligated Pd(0) species have been characterized in a Pd(dba)2/dmim model system. A thorough study of the equilibria involving novel [ArPd(dmim)2X] complexes (X=I, OAc) and the unexpected cationic [ArPd(dmim)3]+ is also reported. The ability of these species to effect the C-H arylation of dmim at room temperature in the presence of acetate is also demonstrated.

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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 report a palladium-catalyzed carbon-carbon bond-forming reaction between aryl iodides and alkenes. In contrast to traditional cross-coupling reactions, two new bonds are formed, and all of the atoms in the starting materials are incorporated into the product. The use of a palladium catalyst with bulky phosphine ligands is found to be crucial for reactivity.

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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 compounds HM(CO)4SnPh3, M = Os (10), Ru (11) are activated in the presence of Pt-(PBut3)2 and Pd(PBut3)2 toward the insertion of PhC 2H into the M-H bond. The compounds PtOs(CO)4-(SnPh 3)(PBut3)[mu-HCC(H)Ph], 12, and PtOs(CO) 4(SnPh3)(PBut3)[mu-H 2CCPh], 13, were obtained from the reaction of 10 with PhC 2H in the presence of Pt(PBut3)2. Compounds 12 and 13 are isomers containing alkenyl ligands formed by the insertion of the PhC2H molecule into the Os-H bond at both the substituted and unsubstituted carbon atoms of the alkyne. Both compounds contain a Pt(PBut3) group that is bonded to the osmium atom and a bridging alkenyl ligand that is pi-bonded to the osmium atom. The reaction of 11 with PhC2H in the presence of Pt(PBut 3)2 yielded the products PtRu(CO)4(SnPh 3)(PBut3)[mu-HC2(H)Ph], 14, and PtRu(CO)4(SnPh3)(PBut3)[mu-H 2C2Ph], 15, which are also isomers similar to 12 and 13. The reaction of 11 with PhC2H in the presence of Pd(PBu t3)2 yielded the product PdRu(CO) 4(SnPh3)(PBut3)[mu-H 2C2Ph], 16. Compound 16 contains a Pd(PBut 3) group bonded to the ruthenium atom and a bridging H 2C2Ph ligand that is pi-bonded to the palladium atom. Compound 10 reacted with Pt(PBut3)2 in the absence of PhC2H to yield the compound PtOs(CO)4(SnPh 3)(PBut3)(mu-H), 17. Compound 17 is a Pt(PBut3) adduct of 10. It contains a Pt-Os bond with a bridging hydrido ligand. Compound 17 reacted with PhC2H to yield 12. Compound 12 reacted with PhC2H to yield the compound PtOs(CO) 3(SnPh3)(PBut3)[mu-HCC(Ph)C(H)C(H) Ph], 18. Compound 18 contains a bridging 2,4-diphenylbutadienyl ligand, HCC(Ph)C(H)C(H)Ph, that is pi-bonded to the osmium atom and sigma-bonded to the platinum atom. Fenkse-Hall molecular orbitals of 17 were calculated. The LUMO of 17 exhibits an empty orbital on the platinum atom that appears to be the most likely site for PhC2H addition prior to its insertion into the Os-H bond.

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

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Functionalised cyclic enol ethers can be recovered with high levels of enantiocontrol after an asymmetric catalytic [1,3]-rearrangement reaction. These compounds can be further elaborated to a series of carbo- and heterocyclic products in good yield and with excellent levels of stereocontrol.

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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 first catalytic lactonization of unactivated aryl C-H bonds with CO2 to afford important phthalides is reported. Notably, this method features high selectivity, excellent functional group tolerance, smooth scalability, and facile product diversification. DFT calculations reveal that a novel insertion of two CO2 into the O-Pd bond of a palladacycle might be the key step, providing great potential and a different perspective for carbonylation with CO2.

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

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A convenient and regioselective synthesis of two series of indolo[2,3-b]quinolines, namely 10H-indolo[3,2-b]quinolines and 6H-indolo[2,3-b]quinolines, has been developed. The synthesis, proceeds in moderate to high yields, involving chemoselective palladium catalyzed Suzuki reaction of 2,3-dihaloquinolines with 2-bromophenylboronic acid, followed by a double Buchwald-Hartwig C-N coupling.

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