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Discovery and Computational Rationalization of Diminishing Alternation in [n]Dendralenes

The [n]dendralenes are a family of acyclic hydrocarbons which, by virtue of their ability to rapidly generate structural complexity, have attracted significant recent synthetic attention. [3]Dendralene through [8]dendralene have been previously prepared but no higher member of the family has been reported to date. Here, we describe the first chemical syntheses of the “higher” dendralenes, [9]dendralene through [12]dendralene. We also report a detailed investigation into the spectroscopic properties and chemical reactivity of the complete family of fundamental hydrocarbons, [3]dendralene to [12]dendralene. These studies reveal the first case of diminishing alternation in behavior in a series of related structures. We also report a comprehensive series of computational studies, which trace this dampening oscillatory effect in both spectroscopic measurements and chemical reactivity to conformational preferences.

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

More research is needed about Tris(dibenzylideneacetone)dipalladium-chloroform

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Phenyl derivatives of antimony(III, V) and bismuth(III, V) in the presence of palladium salts, as C-phenylating agents for methyl acrylate

The C-phenylation of methyl acrylate to methyl cynnamate with Ph 3Sb, Ph3SbX2 (X = Cl, OAc), Ph3Bi, and Ph3BiX2 (X = OAc, O2CEt) in the presence of PdCl2, Pd(OAc)2, Li2PdCl4, NaPd(OAc)Cl2, and Na2Pd(OAc)2Cl2 was studied to show that the reactions with Ph3Sb and Ph 3Sb(OAc)2 are more selective and give higher yields of the target product than those with Ph3Bi and Ph 3Bi(OAc)2, while Ph3M(OAc)2 are preferred over Ph3M. Copper(II) alkanecarboxylate additives have no effect on the yield of methyl cynnamate in the reactions with Ph3Sb.

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

Discovery of Tris(dibenzylideneacetone)dipalladium-chloroform

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An unusual thermodynamic preference of chiral N-arylsulfonyl cis-3-alkyl-2-vinylaziridines over their trans-isomers: Palladium(0)-catalysed equilibration reactions

Palladium (0)-catalysed reactions of N-alkylsulfonyl- or N-arylsulfonyl-3-alkyl-2-vinylaziridines reveal that 2,3-cis-isomers are more stable than the corresponding 2,3-trans-isomers in accord with ab initio calculations.

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

Can You Really Do Chemisty Experiments About Tris(dibenzylideneacetone)dipalladium-chloroform

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PIPERAZINE SUBSTITUTED ARYL BENZODIAZEPINES AND THEIR USE AS DOPAMINE RECEPTOR ANTAGONISTS FOR THE TREATMENT OF PSYCHOTIC DISORDERS

Described herein are antipyschotic compounds of formula (I) wherein, A is an optionally benzo-fused five or six member aromatic ring having zero to three hetero atoms independently selected from N, O, and S; Alk is (C1-4) alkylene optionally substituted with OH, methoxy, ethoxy, or F; Ar is optionally substituted phenyl, naphthyl, monocyclic heteroaromatic, or bicyclic heteroaromatic; R1 is hydrogen or (C1-4) alkyl optionally substituted with OH, OR3, or OCH2CH2OH, wherein R3 is (C1-2) alkyl; R2 is H, (C1-6) alkyl, halogen, fluorinated (C1-6) alkyl, OR4, SR4, NO2, CN, COR4, CONR5R6, SO2 NR5R6, NR5R6, NR5COR4, NR5SO2R4, or optionally substituted phenyl,wherein R4 is hydrogen, (C1-6) alkyl, fluorinated (C1-6) alkyl, benzyl, or optionally substituted phenyl, R5 and R6 are independently hydrogen, (C1-6) alkyl, or optionally substituted phenyl; Z is one or two substituents independently selected from hydrogen, halogen, (C1-6 ) alkyl, fluorinated (C1-6) alkyl, OR7, SR7, NO2, CN, COR7, CONR8R9, SO2 NR8R9, NR8SO2R7, NR8 R9, or optionally substituted phenyl, wherein R7 is hydrogen, (C1-6) alkyl, fluorinated (C1-6) alkyl, benzyl, or optionally substituted phenyl, R8 and R9 are independently hydrogen, (C1-6) alkyl, or optionally substituted phenyl; and salts, solvates, and crystal forms thereof. Also described are the use of the compounds of formula (I) as antagonists of the dopamine D2 receptor and as agents for the treatment of psychosis and bipolar disorders, and pharmaceutical formulations of the compounds of formula (I). Also described are compounds useful as intermediates for the synthesis of the compounds of formula (I).

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

Some scientific research about Tris(dibenzylideneacetone)dipalladium-chloroform

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Solution behavior and structural diversity of bis(dialkylphosphino)methane complexes of palladium

The preparation of dipalladium complexes containing sterically nondemanding diphosphine (P-P) ligands of the type R2PCH2PR2 where R = Me (dmpm) or Et (depm) is reported. Variable-temperature 1H NMR spectra of the PdI2 complexes Pd2X2(dmpm)2 (X = Cl, Br, or I; the P-P ligands in the Pd2 complexes are always bridged, but for convenience, the mu-symbol is omitted) show the complexes to be fluxional in solution, the barriers to a ring-flipping process being DeltaG? = 37.9, 39.0, and 43.2 ¡À 0.9 kJ mol-1 for the chloro, bromo, and iodo complexes, respectively. Treatment of Pd2X2(P-P)2 (X = Cl or Br) with X2 generates the stable, face-to-face PdII2 derivatives trans-Pd2X4(P-P)2, while oxidation of Pd2I2(P-P)2 complexes with I2 generates a new type of symmetrically di-iodo-bridged, five-coordinate complexes Pd2I2(mu-I)2(dmpm)2 and Pd2I2(mu-I)2(depm)2. The molecular crystal structures of four dipalladium(II) complexes are described: trans-Pd2Cl4(dmpm)2¡¤2CHCl 3, trans-Pd2Br4(dmpm)2, and Pd2I2(mu-1)2(dmpm)2. Solution NMR and UV-vis absorption spectra are consistent with the solid-state structures determined by x-ray diffraction. The stability of the dimeric Pd(II) complexes is attributed primarily to ligand steric factors.

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

Brief introduction of 52522-40-4

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Callipeltoside A: Total synthesis, assignment of the absolute and relative configuration, and evaluation of synthetic analogues

The total synthesis of the novel antitumor agent callipeltoside A, as well as several analogues, is accomplished and allows assignment of the stereochemistry not previously established. A convergent strategy is employed wherein the target is dissected into three units – the core macrolactone, the sugar callipeltose, and a cyclopropyl bearing chain. The strategy for the synthesis of the macrolactone derives from employment of diastereoselective aldol reactions that emanate from an 11 carbon piece. The stereochemistry of the latter derives from the chiral pool and two asymmetric reactions – a ketone reduction using CBS-oxazaborolidine and a Pd catalyzed asymmetric allylic alkylation (AAA). The novelty of the latter protocol is its control of regioselectivity as well as absolute configuration. The trisubstituted olefin is generated using an alkene-alkyne coupling to create a trisubustituted olefin with complete control of geometry. The excellent chemo- and regioselectivity highlights the synthetic potential of this new ruthenium catalyzed process. The macrolactonization employs in situ formation of an acylketene generated by the thermolysis of a m-dioxolenone. Two strategies evolved for attachment of the side chain-one based upon olefination and a second upon olefin metathesis. The higher efficiency of the latter makes it the method of choice. A novel one pot olefin metathesis-Takai olefination protocol that should be broadly applicable is developed. The sugar is attached by a glycosylation by employing the O-trichloroacetimidate. This route provided both C-13 epimers of the macrolactone by using either enantiomeric ligand in the Pd AAA reaction. It also provided both trans-chlorocyclopropane diastereomers of callipeltoside A which allows the C-20 and C-21 configuration to be established as S and R, respectively. The convergent nature of the synthesis in which the largest piece, the macrolatone, require only 16 linear steps imparts utility to this strategy for the establishment of the structure-activity relationship. Initial biological testing demonstrates the irrelevance of the chloro substituent and the necessity of the sugar.

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

Brief introduction of 52522-40-4

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The first evidence of insertion of isocyanide into a metal-sulfur bond: Catalytic and stoichiometric behavior of isocyanide and thiolate ligands on palladium and platinum

The first evidence of insertion of isocyanide into M-S bond has been demonstrated. Tetrakis-(triphenylphosphine)palladium [Pd(PPh3)4] catalyzes the reaction of a disulfide (ArS)2 (1) with an isocyanide ArNC (2) (Ar = 4- MeC6H4) to produce the adducts (ArS)(C=NAr)(m)(SAr). The reactions of 1:m adducts with 2 are also catalyzed by the Pd complex to afford 1:k adducts (k ? m). The mechanistic study reveals that the complex Pd- (SAr)2(CNAr)(PPh3) (8) is a resting state for giving 1:1 adduct and converted into 1:1 adduct 3 (m = 1) in the presence of another 1 equiv of 1. The stoichiometric reaction of 3 with Pd(PPh3)4 provides 8, but the stoichiometric oxidative addition of l:m adducts (m = 2, 3, 4) to Pd(PPh3)4 did not give any definitive Pd(II) species. These facts reveal that both the insertion of isocyanide(s) into Pd-S bond and the reductive elimination of 1:m adduct are reversible. The study on reactivities of isocyanide and thiolate ligands on platinum, including the X-ray crystallographic analysis of the imidoyl platinum trans-Pt[(C=NAr)2SAr](SAr)(PPh3)2 (21) obtained by the oxidative addition of the C-S bond of 1:2 adduct 4 (m = 2) to Pt(PPh3)4 has also been reported.

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

Top Picks: new discover of Tris(dibenzylideneacetone)dipalladium-chloroform

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Oxidative addition of allyl and propargyl halides on palladium(0) complexes bearing bidentate ligands with quinolinic structure

Abstract We have synthesized three Pd(0) complexes stabilized by the olefin dimethyl fumarate and bidentate ligands based on the quinoline frame with thioetheric or diphenylphosphine function. We have reacted all the synthesized complexes with allyl or propargyl halides and isolated the products of the resulting oxidative addition. The solid state structures in the case of a Pd(0) derivative 1C and of the allenyl complexes 2Af and 2Ag have been resolved and we performed some computational calculations in order to establish whether the formation of allenyl or propargyl derivative as reaction products could be influenced by their reciprocal thermodynamic stability or by kinetic reasons. In this respect we have also carried out some kinetic investigations and hypothesized a plausible mechanism of the oxidative addition.

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

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BRIDGED PIPERIDINE DERIVATIVES

The present invention relates to a compound of formula (I), wherein Het Ar is a five or six membered hetaryl group, containing one, two or three heteroatoms, selected from N, O or S; R1 is hydrogen, lower alkyl, lower alkyl substituted by halogen, halogen, or lower alkoxy; R2 is lower alkyl substituted by halogen, -CH2-C3-6-cycloalkyl, substituted by one or two substituents, selected from lower alkyl substituted by halogen or halogen, or is lower alkenyl substituted by halogen; R3 is hydrogen, lower alkyl substituted by halogen, lower alkyl, halogen, C3-6-cycloalkyl or lower alkyl substituted by hydroxy; n is 1 or 2; for n = 2, R1 can be independent to each other; Y is CH or N; or to a pharmaceutically active acid addition salt thereof, to a racemic mixture or its corresponding enantiomer and/or optical isomer and/or stereoisomer thereof. The compounds may be used for the treatment of Alzheimer’s disease, cerebral amyloid angiopathy, hereditary cerebral hemorrhage with amyloidosis, Dutch-type (HCHWA-D), multi-infarct dementia, dementia pugilistica or Down syndrome.

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

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Palladium-Catalyzed [4+2] and [5+2] Annulation for the Synthesis of Tetrahydroquinolines and 1,4-Benzoxazepines

Palladium-catalyzed [4+2] and [5+2] annulations of propargyl carbonates with malonate-tethered anilines and 2-aminobenzylic alcohols were developed, giving the corresponding tetrahydroquinolines and 1,4-benzoxazepines, respectively, in good to excellent yields.

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