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The present invention relates to a process for the regioselective synthesis of compounds of the formula (I), wherein R0; R1; R2; R3; R4; R5; R6; A1; A2; A3; A4, Q, T and J have the meanings indicated in the claims. The present invention provides a direct transition metal catalyzed process to a wide variety of multifunctional N-aminoindole or N-amino- azaindoles of the formula (I) from 2-halo-phenylacetylenes or (2-sulfonato)phenyl- acetylenes and N,N-disubstituted hydrazines, useful for the production of pharmaceuticals, diagnostic agents, liquid crystals, polymers, herbicides, fungicidals, nematicidals, parasiticides, insecticides, acaricides and arthropodicides.

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

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Enantioselective Pd(0)-catalyzed C-H functionalizations of ketene aminal phosphates provide isoindoline scaffolds with high enantioselectivity at ambient temperature. The high level of enantiocontrol is enabled by a tailored monodentate electron-rich phosphine ligand featuring a point-chiral phospholane module and a bulky atropchiral binaphthyl backbone.

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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 straightforward route toward construction of alpha-quaternary chiral beta-lactam moiety via Rh(II)/Pd(0)-catalyzed stereoselective relay catalytic reaction is reported. This asymmetric dual relay catalysis involves Rh(II)-catalyzed enantioselective intramoluecular C-H insertions of alpha-diazoamides, and sequential Pd(0)-catalyzed diastereoselective intermolecular allylic alkylation. Under mild reaction conditions, a broad range of alpha-quaternary allylated chiral beta-lactams have been synthesized in high yields (up to 99%) with excellent stereoselectivities [up to diastereomeric ratio (dr) >99:1, up to 98% enantiomeric excess (ee)].

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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 asymmetric allylic alkylation (AAA), which features employing active allylic substrates, has historical significance in organic synthesis. The allylic C-H alkylation is principally more atom- and step-economic than the classical allylic functionalizations and thus can be considered a transformative variant. However, asymmetric allylic C-H alkylation reactions are still scarce and yet underdeveloped. Herein, we have found that Z/E- and regioselectivities in the Pd-catalyzed asymmetric allylic C-H alkylation of 1,4-dienes are highly dependent on the type of nucleophiles. A highly stereoselective allylic C-H alkylation of 1,4-dienes with azlactones has been established by palladium-chiral phosphoramidite catalysis. The protocol proceeds under mild conditions and can accommodate a wide scope of substrates, delivering structurally divergent alpha,alpha-disubstituted alpha-amino acid surrogates in high yields and excellent levels of diastereo-, Z/E-, regio-, and enantioselectivities. Notably, this method provides key chiral intermediates for an efficient synthesis of lepadiformine marine alkaloids. Experimental and computational studies on the reaction mechanism suggest a novel concerted proton and two-electron transfer process for the allylic C-H cleavage and reveal that the Z/E- and regioselectivities are governed by the geometry and coordination pattern of nucleophiles.

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

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o-Iodophenols and o-iodoaniline derivatives react with terminal alkynes under 1 atm of CO in the presence of pyridine and catalytic amounts of Pd(OAc)2 to generate coumarins and 2-quinolones, respectively, as the only products. Terminal alkynes bearing alkyl, aryl, silyl, hydroxyl, ester and cyano substituents are effective in these processes affording the desired products in moderate yields. The formation of coumarins and 2-quinolones in this process is in stark contrast with all previously described palladium-catalyzed reactions of o-iodophenols or o-iodoanilines with terminal alkynes and CO, which have afforded chromones and 4-quinolones. Moreover, under our reaction conditions terminal alkynes insert into the carbon-palladium bond instead of undergoing a Sonogashira-type coupling as confirmed by an isotope labeling experiment.

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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 generation of PNP compounds bearing different diarylphosphine groups were prepared and used as ligands in palladium-catalysed Suzuki cross-coupling reactions. Rates of oxidative addition of iodobenzene to (PNP)Pd[o] complexes were measured using UV spectroscopy. Synergistic effects between the N- and P- substituents were identified and correlated in redox and catalytic chemistry.

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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 facile and site-selective C-H bond fluorination of phenols using removable 2-pyridyloxy group as an auxiliary was developed. Alternatively, late-stage C-H bond fluorination of bioactive 2-phenoxyl nicotinate derivatives and diflufenican were also feasible under the present strategy.

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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 series of shape-persistent macrocycles featuring both m-phenylene and 2,5-thiophene linkers has been synthesized, including an example where they bridge electron-rich (veratrole) and electron-poor (phthalimide) units. Charge transfer in this “push-pull macrocycle” has been investigated by UV-vis and fluorescence spectroscopies and DFT calculations. The effect of pairing structurally distinct conjugated bridges is discussed in the context of acyclic and symmetrical macrocyclic analogs.

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

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Traditional materials for application in organic light emitting diodes (OLEDs) are primarily based on small molecules and polymers, with much fewer examples of intermediate molecular weights materials. Our interest lies in this intermediate molecular weight range, specifically in hybrids based on 3-dimensional silsesquioxane (SSQ) cores that represents a new class of versatile materials for application in solution processable OLEDs. We report here SSQ based hybrids (P8-OVS and P14-OVS) that are easily prepared in one high-yield step from the Heck coupling of commercially available 1-bromopyrene with octavinyl-SSQ. The resulting materials offer numerous advantages for OLEDs including amorphous properties, high-glass-transition temperatures (Tg), low polydispersity, solubility in common solvents, and high purity via column chromatography. Solution processed OLEDs prepared from P8-OVS provide blue-green emission with external quantum efficiencies, current efficiencies, maximum brightness, and turn-on voltages of 2.63%, 8.28 cd/A, 36183 cd/m2, and 3.1 V, respectively. 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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A compound of formula I STR1 wherein X is sulfur or CH2 ; R1 is hydrogen, hydroxy, amino, C1-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, phenyl optionally substituted with one to three C1-6 alkyl, C1-6 alkyloxy or hydroxy, C1-6 alkylthio, phenylthio optionally substituted with one to three C1-6 alkyl or C1-6 alkyloxy on the phenyl ring, phenylmethyloxy optionally substituted with one to three C1-6 alkyl or C1-6 alkyloxy on the phenyl ring, 1-morpholino, C1-6 alkyloxy, C2-6 alkenylmethyloxy, C3-6 alkynylmethyloxy, C1-6 alkylamino, C1-6 dialkylamino or a radical selected from the group consisting of STR2 in which n is 0 to 3, R5 is C1-6 alkyl or hydrogen, and R3 and R4 are independently C1-6 alkyl; R2 is hydrogen, a conventional amino protecting group or an acyl group; R0 is hydrogen or a conventional carboxy protecting group, or –CO2 R0 taken together forms a physiologically hydrolyzable ester; or pharmaceutically acceptable salts or solvates thereof.

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