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The synthesis of conjugated polymers from direct (hetero)arylation polymerization (DHAP) has been achieved for the first time using biphasic water/toluene conditions. This protocol is robust enough to form polymers even when air is introduced in the system. General reactivity is demonstrated for a single set of polymerization conditions with thienyl- or phenyl-based substrates, whether they are electron-rich or electron-poor. Complete characterization from differential scanning calorimetry and 1H NMR and UV-vis-NIR spectroscopies is presented, demonstrating this DHAP protocol offers comparable or better properties than the very best values published thus far. High molecular weights are obtained, showcasing the perfect equilibrium of reactivity and selectivity attained with this method. Moreover, this efficient and versatile methodology, which also uses low-cost, “wet” reagents, is scalable and done at ambient pressure.

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

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Based on the [2-(2-nitrophenyl)propoxy]carbonyl (nppoc) group, six new photolabile protecting groups (2, 8, 9b, 16b, 25b, and 26), each covalently linked to a 9H-thioxanthen-9-one (Tx) unit functioning as an intramolecular triplet sensitizer, were synthesized. Linkers were introduced between the Me group or the aromatic ring of nppoc and the 2-position of Tx by means of classical organic synthesis combined with Pd catalyzed C-C coupling reactions. The new photolabile protecting groups to be used in light-directed synthesis of DNA chips were attached to the 5?-O-atom of thymidine via a carbonate linkage, giving rise to the caged nucleosides 7, 11, 13, 19, 20, and 30.

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

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Reactions of sodium tetraarylborates and arylboronic acids with acyl chlorides in the presence of palladium salts afford non-symmetrical ketones in high yields under mild conditions.

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

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Several 3-alkylaryl mimics of the enol intermediate in the reaction catalyzed by type II dehydroquinase were synthesized to investigate the effect on the inhibition potency of replacing the oxygen atom in the side chain by a carbon atom. The length and the rigidity of the spacer was also studied. The inhibitory properties of the reported compounds against type II dehydroquinase from Mycobacterium tuberculosis and Helicobacter pylori are also reported. The binding modes of these analogs in the active site of both enzymes were studied by molecular docking using GOLD 5.0 and dynamic simulations studies.

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

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Treatment of [Ir(ppy)2(mu-Cl)]2 and [Ir(ppy) 2(dtbpy)][OTf] (ppy = 2-(2?-pyridyl)phenyl; dtbpy = 4,4?-di-tert-butyl-2,2?-bipyridine; OTf = triflate) with pyridinium tribromide in the presence of Fe powder led to isolation of [Ir(4-Br-ppy)(mu- Br)]2 (1) and [Ir(4-Br-ppy)2(dtbpy)][OTf] (2), respectively. Pd-catalyzed cross-coupling of 2 with RB(OH)2 afforded [Ir(4-R-ppy)2(dtbpy)][OTf] (R = 4?-FC6H4 (3)), 4?-PhC6H4 (4), 2?-thienyl (5), 4?-C6H4CH2OH (6). Treatment of 4 with B2(pin)2 (pin = pinacolate) afforded [Ir{4-(pin)B-ppy} 2(dtbpy)][OTf] (7). The alkynyl complexes [Ir(4-PhCC-ppy) 2(dtbpy)][OTf] (8) and [Ir{4-Me2(OH)CC-ppy}(4-Br-ppy) (dtbpy)][OTf] (9) were prepared by cross-coupling of 2 with PhCCSnMe3 and Me2C(OH)CCH, respectively. Ethynylation of [Ir(fppy) 2(dtbpy)][OTf] (fppy = 5-formyl-2-(2?-pyridyl)phenyl) with Ohira’s reagent MeCOC(N2)P(O)(OEt)2 afforded [Ir{5-HCC-ppy}2(dtbpy)][OTf] (10). The solid-state structures of 2, 5, 7, and 10 have been determined.

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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 syntheses, properties, and biological applications of the Peroxysensor family, a new class of fluorescent probes for hydrogen peroxide, are presented. These reagents utilize a boronate deprotection mechanism to provide high selectivity and optical dynamic range for detecting H2O2 in aqueous solution over similar reactive oxygen species (ROS) including superoxide, nitric oxide, tert-butyl hydroperoxide, hypochlorite, singlet oxygen, ozone, and hydroxyl radical. Peroxyresorufin-1 (PR1), Peroxyfluor-1 (PF1), and Peroxyxanthone-1 (PX1) are first-generation probes that respond to H2O2 by an increase in red, green, and blue fluorescence, respectively. The boronate dyes are cell-permeable and can detect micromolar changes in H2O2 concentrations in living cells, including hippocampal neurons, using confocal microscopy and two-photon microscopy. The unique combination of ROS selectivity, membrane permeability, and a range of available excitation/emission colors establishes the potential value of PR1, PF1, PX1, and related probes for interrogating the physiology and pathology of cellular H2O2.

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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 synthesis of extended heteroarenes via the acid-promoted dehydrocyclisation of arylamino-anthraquinones is examined as an approach to highly conjugated electron-acceptor materials and eventually to heterographene nanoribbons. Whilst the latter perspective is found to remain challenging, the former is exemplified by the synthesis of extended tetraazaheterocycles bearing solubilising alkyl substituents. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2012.

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

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Single crystal X-ray diffraction analysis of Pd(O2CCF2CF3-O)2(dppf) 1 shows that one of the two unidentate fluoropropanoates shows a rare bonding behavior with significant ? character for the C=Ocoord bond whereas the C-Opendant bond is long and bears a basic function. Complex 1 serves as a metalloligand towards AgO2CCF2CF3 to give PdAg(mu-O2CCF2CF3)2(O2CCF2CF3-O)(dppf) 2, which is fluxional in solution showing interchanges of the bridging and unidentate fluoropropanoate groups. Being an unusually stable Pd(II) carboxylate, 1 also serves an effective entry to mixed-metal carboxylates.

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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 bis(diphenylphisphino)ferrocene (dppf) derived palladium analogue of [PdCl2(dppf)] on reaction with the sodium salt of pyridyl/pyrimidyl selenolate yielded mononuclear cis configured complex [Pd(SeAr)2(dppf)] (Ar = C5H4N, C4H(4,6-Me)2N2), as did the platinum precursor [PtCl2(dppf)] with methyl substituted pyrimidyl salt giving [Pt{SeC4H(4,6-Me)2N2}2(dppf)]. In contrast, the reaction of platinum precursor with the sodium salt of pyridylselenolate gave two different complexes [Pt2(mu-SeC5H4N)2(dppf)2]2+ and [Pt(Cl)(SeC5H4N)(dppf)] depending in the reaction solvent. These complexes were characterized by elemental analysis and NMR (1H, 31P) spectroscopy. The molecular structure of [Pt{SeC4H(4,6-Me)2N2}2(dppf)] was established by single crystal X-ray diffraction analysis.

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

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Bench-stable solid triorganoindium compounds have been prepared by coordination with 4-(dimethylamino)pyridine (DMAP). The solid R3In(DMAP) complexes are obtained from the corresponding solution of R3In in quantitative yield and can be stored for up to several weeks. These reagents show excellent reactivity in palladium-catalyzed cross-coupling reactions with organic electrophiles.

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