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The specification of the formula 1 compound and organic light emitting number including […] substrate. (by machine translation)

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

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Application of an in situ generated bulky palladium(II) hydride catalyst obtained from a 1:1:1 mixture of Pd(dba)2, P(tBu)3, and isobutyryl chloride provides an efficient protocol for the isomerization and migration of a variety of olefins. In addition to the isomerization of (Z)- to (E)-olefins, the conjugative migration of allylbenzenes, allyl ethers, and amines was effectively achieved in near-quantitative yields and with excellent functional group tolerance. Catalyst loadings in the range of 0.5-1.0 mol % were typically applied, but even loadings as low as 0.25 mol % could be achieved when the reactions were performed under neat conditions. More interestingly, the investigated catalyst proved to be selective for converting terminal alkenes to 2-alkenes. This one-carbon migration process for monosubstituted olefins provides an alternative catalyst, which bridges the gap between the allylation and propenylation/vinylation protocols. Several substrates, including homoallylic alcohols and amines, were selectively transformed into their corresponding 2-alkenes, and examples using enantiomerically enriched substrates provided products without epimerization at the allylic stereogenic carbon centers. Finally, some mechanistic investigations were undertaken to understand the nature of the active in situ generated Pd-H catalyst. These studies revealed that the catalytic system is highly dependent on the large steric demand of the P(tBu)3 ligand. The use of an alternative ligand, cataCXium PinCy, also proved effective for generating an active catalyst, and it was demonstrated in some cases to display better selectivity for the one-carbon shifts of terminal olefins. A possible intermediate involved in the preparation of the active catalyst was characterized by its single-crystal X-ray structure, which revealed a monomeric tricoordinated palladium(II) acyl complex, bearing a chloride ligand.

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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 present paper describes a synergistic effect in the Pdcatalyzed SuzukiMiyaura cross-coupling reaction. The chemoselective cross-coupling reaction of (diborylmethyl)trimethylsilane and aryl halides proceeded at room temperature when a silver salt and KOH were added. The reaction gave benzylboronate derivatives bearing a trimethylsilyl group at the benzylic position.

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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 palladium-catalyzed multicomponent method for the synthesis of beta-lactams from imines, aryl halides, and CO has been developed. This transformation proceeds via two tandem catalytic carbonylation reactions mediated by Pd(PtBu3)2 and provides a route to prepare these products from five separate reagents. A diverse range of polysubstituted beta-lactams can be generated by systematic variation of the substrates. This methodology can also be extended to the use of iodo-substituted imines to produce novel spirocyclic beta-lactams in good yields and selectivity.

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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 invention relates to pyrazolyl-based carboxamide compounds useful as ICRAC inhibitors, to pharmaceutical compositions containing these compounds and to these compounds for the use in the treatment and/or prophylaxis of diseases and/or disorders, in particular inflammatory diseases and/or inflammatory disorders.

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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 Pd-catalyzed carbonylation of cyclic beta-chloro enones using simple phosphine ligands is described. Screening identified P(Me)(t-Bu)2 as the most general ligand for an array of chloro enone electrophiles. The reaction scope has been evaluated on a milligram scale across 80 examples, with excellent reactivity observed in nearly every case. Carbonylation can be achieved even in the presence of potentially sensitive or inhibitory functional groups, including basic nitrogens as well as aryl chlorides or bromides. Twenty examples have been run on a gram scale, demonstrating scalability and practical utility. Using P(Me)(t-Bu)2, the reaction rate depends on both nucleophile and electrophile identity, with completion times varying between 3 and >18 h under a standard set of conditions. Switching to P(t-Bu)3 for the carbonylation of 3-chlorocyclohex-2-enone with methanol results in a dramatic rate increase, enabling effective catalysis with kinetics consistent with rate-limiting mass transfer. Stoichiometric oxidative addition of 3-chlorocyclohex-2-enone and 3-oxocyclohex-1-enecarbonyl chloride to both Pd[P(t-Bu)3]2 and Pd(PCy3)2 has enabled characterization and isolation of several potential catalytic intermediates, including Pd-vinyl and Pd-acyl species supported by P(t-Bu)3 and PCy3 ligands. Monitoring the oxidative addition of 3-chlorocyclohex-2-enone to Pd(PCy3)2 by NMR spectroscopy indicates that coordination of the alkene precedes oxidative addition. As a result of these studies, methyl 3-oxocyclohex-1-enecarboxylate has been synthesized via Pd-catalyzed carbonylation of 3-chlorocyclohex-2-enone in 90% yield on a 60 g scale with only 0.5 mol % catalyst loading.

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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 have performed a series of stoichiometric studies in order to identify viable steps for a hypothetical catalytic cycle for the palladium-mediated carbonylative coupling of an aryl bromide with TMSCF3. Our work revealed that benzoyl Pd(II) complexes bearing Xantphos or tBu3P as the phosphine ligands, which are generated from the corresponding PdII(Ph)Br complexes exposed to stoichiometric 13CO from 13COgen, were unable to undergo transmetalation and reductive elimination to trifluoroacetophenone. Instead, in the presence of base and additional CO, these organometallic complexes readily underwent reductive elimination to the acid fluoride. Attempts to determine whether the acid fluoride could represent an intermediate for acetophenone production were unrewarding. Only in the presence of a boronic ester did we observe some formation of the desired product, although the efficiency of transformation was still low. Finally, we investigated the reactivity of four phosphine-ligated PdII(Ph)CF3 complexes (Xantphos, DtBPF, tBu3P, and triphenylphosphine) with carbon monoxide. With the exception of the tBu3P-ligated complex, all other metal complexes led to the facile formation of trifluoroacetophenone. We also determined in the case of triphenylphosphine that CO insertion occurred into the Pd-Ar bond, as trapping of this complex with n-hexylamine led to the formation of n-hexylbenzamide.

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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 oxidative addition of PhX (X ) I, Br, Cl) to the complexes Pd(P tBu3)2 (1), Pd(1-AdPtBu2)2 (2), Pd(CyPtBu2)2 (3), and Pd(PCy3) 2 (4) (1-Ad = 1-adamantyl, Cy = cyclohexyl) was studied todetermine the effect of steric properties on the coordination number of the species that undergoes oxidative addition and to determine whether the type of halide affects the identity of this species. The kinetic dat a imply that the number of phosphines coordinated to the complex that reacts in the irreversible step of the oxidative addition process for complexes 1-4 depends more on the halide than on the steric properties of the ligands. The rate-limiting step of the oxidative addition of PhI occurred with L2Pd(0) in all cases, as determined by the lack of dependence of kobs on [PtBu3], [1-AdPtBu2], or [CyPtBu2] and the inverse dependence of the rate constant on [PCy3] when the reaction was initiated with Pd(PCy3)3. The irreversible step of the oxidative addition of PhCl occurred with a monophosphine species in each case, as signaled by an inverse dependence of the rate constant on the concentration of ligand. The irreversible step of the oxidative addition of PhBr occurred with a bisphosphine species, as signaled by the zeroth-order or small dependence of the rate constant on the concentration of phosphine. Thus, the additions of the less reactive chloroarenes occurthrough lower-coordinate intermediates than additions of the more react ive haloarenes.

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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 present invention refers to formula 1 compounds and organic light emitting organic layer including said compound number […] substrate. (by machine translation)

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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 range of 2,5-diarylated thiophenes were synthesised as small molecule mimetics of the alpha-helix to modulate the amyloidogenesis and cytotoxic effect of islet amyloid polypeptide (IAPP). 3-Substituted thiophene-2-carboxylic acids were used as key intermediates and functionalised by palladium decarboxylative cross-coupling and direct C=H activation successively with overall yields ranging from 23 to 95 %. The effect of the ligands on IAPP amyloid fibril formation was evaluated with the thioflavina T (ThT) fluorescence-based assay. Furthermore, the capacity of these compounds to inhibit the cytotoxic effect of IAPP was assessed using beta-pancreatic cells. A twist manipulated: A range of 2,5-diarylated thiophenes was synthesised as small molecule mimetics of the alpha-helix to modulate the amyloidogenesis and cytotoxic effect of islet amyloid polypeptide (IAPP; see scheme). The effect of the ligands on IAPP amyloid fibril formation was evaluated. Furthermore, the capacity of these compounds to inhibit the cytotoxic effect of IAPP was assessed using beta-pancreatic cells. Copyright

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