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3-(Hetero)aryl substituted indoles, 7-azaindoles, and pyrroles can be obtained in a very concise fashion via a one-pot Masuda borylation-Suzuki coupling sequence. The concise total syntheses of the marine natural products meridianins A (5) and G (4i) nicely illustrate the utility of this methodology.

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

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Supramolecular chiral induction has been observed in five dinuclear triple-stranded helicates composed entirely of achiral components. Three different chiral cations were found to be very effective at inducing high levels of enantiomeric enrichment in racemic mixtures of the helicates. The mechanism of intermolecular chiral induction in one cation-helicate pair, s-nic/K 6[Ga2L13], has been elucidated through circular dichroism spectroscopy, X-ray crystallography, and one and two-dimensional NMR spectroscopy (s-nic = N-methyl-s-nicotinium, H 4L1 = 1,4-bis(2?,3?-dihydroxybenzamido) phenylene).

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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 application of borylated N-aryl sulfoximines as newly designed synthetic building blocks in Suzuki-type cross coupling reactions offers rapid access to a wide range of N-biaryl derivatives with potential relevance for medicinal chemistry and crop protection in good to excellent yields (up to 98%). (Figure presented.).

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

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In search of prospective agents against infectious diseases, 1,1?-bis(diphenylphosphino)ferrocene pyridine-2-thiolato-1-oxide M(II) hexafluorophosphate compounds [M(mpo)(dppf)](PF6), where M = palladium or platinum, were synthesized and fully characterized in the solid state and in solution using experimental and DFT computational techniques. The compounds are isomorphous and the M(II) transition metal ions are in a nearly planar trapezoidal cis-coordination bound to the pyridine-2-thiolato-1-oxide (mpo) and to the 1,1?-bis(diphenylphosphino)ferrocene molecules, both acting as bidentate ligands. Both compounds showed high cytotoxic activity on Trypanosoma cruzi and Mycobacterium tuberculosis (MTB) and acceptable selectivities towards MTB, but good to excellent selectivity index values as anti-T. cruzi compounds. The inclusion of the ferrocene moiety (dppf ligand) improved the selectivity towards the parasite when compared to the previously reported [M(mpo)2] complexes. Related to the probable mechanism of action of the complexes, molecular docking studies on modelled T. cruzi NADH-fumarate reductase (TcFR) predicted that both be very good inhibitors of the enzyme. The effect of the compounds on the enzyme activity was experimentally confirmed using T. cruzi protein extracts. According to all obtained results, both [M(mpo)(dppf)](PF6) compounds could be considered prospective anti-trypanosomal agents that deserve further research.

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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 new class of infinite coordination polymers (CP) was synthesized using a tetrahedral tetrakis[4-(4?-phenyl-2,2?:6?,2??- terpyridine)phenyl]methane ligand as an organic node to direct the three-dimensional growth of the network and MII (M = Zn, Fe, Ni, and Ru) ions as inorganic linkers, an approach that is the opposite of the metal-as-a-node strategy used in the construction of metal-organic frameworks (MOFs). The unusual rod-like morphology of the resulting microporous materials can be tuned via solvents and reaction conditions. The covalent entrapment of a [Ru(tpy)2]2+ moiety in the skeleton of the 3D-network enables the Ru-CP to exhibit room-temperature 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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The effects of reducing the molecular weight of the antileishmanial compound DB766 on DNA binding affinity, antileishmanial activity and cytotoxicity are reported. The bis-arylimidamides were prepared by the coupling of aryl S-(2-naphthylmethyl)thioimidates with the corresponding amines. Specifically, we have prepared new series of bis-arylimidamides which include 3a, 3b, 6, 9a, 9b, 9c, 13, and 18. Three compounds 9a, 9c, and 18 bind to DNA with similar or moderately lower affinity to that of DB766, the rest of these compounds either show quite weak binding or no binding at all to DNA. Compounds 9a, 9c, and 13 were the most active against Leishmania amazonensis showing IC50 values of less than 1 muM, so they were screened against intracellular Leishmania donovani, showing outstanding activity with IC 50 values of 25-79 nM. Despite exhibiting little in vitro cytotoxicity these three compounds were quite toxic to mice.

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

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Two series of optically active, cleft-type dendritic receptors (dendroclefts) for carbohydrate recognition were prepared by attaching Frechet-type dendrons via ethynediyl linkers to a core consisting of one or two 1,1′-binaphthalene-2,2′-diyl phosphate moieties. Sugar substrates were expected to bind via bidentate ionic H-bonding of two OH groups to the phosphodiester core and, additionally, to undergo van der Waals and CH···pi interactions with the aromatic rings of the surrounding dendritic wedges. The synthesis of the dendritic receptors G-1-(S)-1, G-2-(S)-2, and G- 3-(S)-3 (Fig. 1; G-x = dendritic generation) with a single binaphthalene core started from 3,3′-diethynylated MOM-protected (MOM = methoxymethyl) 1,1′- binaphthalene-2,2′-diol (S)-13 to which the Frechet-type dendrons of generations 1-3 were attached via Sonogashira cross-coupling (Scheme 3). MOM- Ether deprotection followed by phosphodiester formation and ion exchange provided the targeted receptors. By a similar route, receptor G-1-(S)-23 with dendritic wedges capped with oligoether groups was obtained (Scheme 4). In receptor G-1-(S)-26, the ethynediyl linker was omitted, and, in its synthesis, the dendritic wedges were attached to MOM-protected 3,3′-diiodo- 1,1′-binaphthalene-2,2′-diol by Suzuki cross-coupling (Scheme 5). The synthesis of the dendritic receptors G-2-(S,S)-42 and G-1-(S,S)-43 with two binaphthalene moieties at the core (Fig. 3) started from diethynylated (S,S)- 39 and (S,S)-33, which contain two MOM-protected 1,1′-binaphthalene-2,2′-diol moieties bridged by p-phenylene or buta-1,3-diynediyl linkers, respectively, and was completed by attachment of the dendritic wedges by Sonogashira coupling, MOM-ether deprotection, phosphodiester formation, and ion exchange (Schemes 9 and 10). By an alternative route, the C-frame of receptor G-2- (S,S)-41 was prepared by coupling the dendron to dialkynylated 1,1′- binaphthalene (S)-44, followed by oxidative Glaser-Hay coupling (Scheme 8). For control studies, the non-dendritic reference receptors (S)-4 and (S)-5 (Fig. 1) with one and (S,S)-31 and (S,S)-32 (Fig. 2) with two 1,1′- binaphthalene-2,2’diyl phosphate moieties were also prepared. 1H-NMR Complexation studies with the dendritic receptors containing one binaphthalene core and octyl glycosides 53 – 55 in CD3CN and CDCl3 (Tables 2 – 4) revealed that ionic H-bonding between the phosphodiester core in the dendritic receptors and the sugar OH groups provides the major driving force for stoichiometric 1:1 host-guest association. A smaller, yet significant contribution to the binding free enthalpy was also provided by interactions between the sugar guests and the dendritic wedges. Binding selectivity was weak in all cases, and only small changes in association strength were observed as a function of dendritic generation. In studies with the dendritic receptors, which contain two binaphthalene moieties at the core, higher-order complex stoichiometries prevented the determination of quantitative binding data. As a result of unfavorable steric interactions between the dendritic wedges, these flexible receptor systems apparently avoid adopting the ‘syn’- conformation with convergent phosphodiester sites that is required for efficient 1:1 host-guest complexation.

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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 Pd(ii)-catalyzed homo-coupling of Au(i)-aryls is reported. The reaction is driven by a Pd(0)/Au(i) redox reaction that generates a gold mirror and Pd(ii), and illustrates one of the challenges for developing dual catalytic Au-Pd systems.

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

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Long reaction period (dozens of hours) is often required for the synthesis of conjugated polymers by palladium-catalyzed Suzuki polymerization reaction. This work shows that microwave can accelerate Suzuki polymerization to realize the ultra-rapid synthesis of conjugated polymers, here poly(9,9-dihexylfluorene) s (PDHFs) as an example. The effects of reaction conditions on the polymerization have been systematically investigated, including the mode of microwave irradiation, microwave power, reaction temperature, reaction time, solvents, catalyst species, and catalyst concentrations. Compared with the conventional heating method (oil bath) for the synthesis of PDHFs (48 h, M w = 20,000 g/mol), Suzuki polymerization under optimized microwave condition can yield PDHFs with higher molecular weight (Mw = 40,000 g/mol) in a much shorter time (14 min). The structures of obtained PDHFs samples are fully characterized spectroscopically, demonstrating well-defined PDHFs have been prepared through microwave-assisted (MA) Suzuki polymerization reaction. In addition, the mechanism of MA Suzuki polymerization is proposed preliminarily. 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013 Microwave-assisted (MA) Suzuki polymerization for polyfluorenes has been systematically investigated. It is very important to control the reaction conditions in order to depress the formation of cross-linked products. Compared with oil bath heating, MA synthesis can greatly reduce the reaction time from 48 h (oil bath heating) to 14 min, and resultant polymer products show the higher molecular weight of 40,000 under optimized conditions. 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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Fluorescent and luminescent reporters that signal molecular events of interest by modulating the ratio of peaks in their emission profile have advantages over reporters that simply modulate their emission intensity, since ratiometric measurement is concentration-independent and allows them to be effective in complex contexts, such as living cells or sensor microarrays. We herein describe a general platform for the design of ratiometric probes based on a heterometallic Tb3+/Eu3+ bis-lanthanide ensemble, consisting of a mixture, or “cocktail”, of otherwise identical heterometalated chelates. The chelate contains an organic photon antenna that sensitizes the Tb3+/Eu3+ luminescence. The contributions of the two metals to the composite luminescence spectrum can be tuned to the same relative scale by adjusting the stoichiometry of the cocktail, allowing subtle changes in their ratio to be accurately measured. Importantly, the ratio responds to chemical and environmental changes experienced by the photon antenna, making the system an ideal platform for the design of chemical and enzymatic probes. As proofs of concept, we describe a ratiometric probe for esterase activity and a polarity-responsive ratiometric sensor.

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