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Diazadienes as control ligands in homogeneous catalysis XVIII. Palladacyclopentadienes and platinacyclopentadienes and the co-cyclotrimerization of various alkynes

Bis(dibenzylidene acetone)palladium reacts readily with N-aryl diazadienes (dad = ArN=CRCR=NAr) and two moles of dialkyl acetylenedicarboxylates EC<*>CE (E = COOR) to form the palladacyclopentadienes (dad)PdCE=CECE=CE (2a-h).With a propiolic ester HC<*>CE the corresponding complex (dad)PdCH=CECE=CH 3 is also formed in small yield.An eta2-alkyne complex 4 is obtained from the very bulky dad tBuN=CHCH=NtBu.The platinacyclopentadiene analogues of 2, (dad) (5) have been prepared, but unlike the others are inactive in catalysis.The acetylenic diesters readily undergo cyclotrimerization with 2 as catalyst.Depending on the nature of the substituents, numerous alkynes R’C<*>CR” undergo a catalytic cyclo-cotrimerization with two moles of the diester EC<*>CE to form a number of interestingly substituted benzenes.In the case of propargylic alcohols benzolactones are formed via a transesterification reaction during the catalysis.For phenylacetylene and EC<*>CE not only the corresponding biphenyl derivative 8 but also the linear Z and E 1 : 2-addition products have been isolated.

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

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Intramolecular C – H arylation reaction catalyzed synthesis of chiral phosphine compound and its preparation method (by machine translation)

The invention discloses a intramolecular C – H arylation reaction catalyzed synthesis of chiral phosphine compound, characterized in that the chemical formula of compound of general formula states the chiral phosphine as shown in I, wherein R1 C is hydrogen or1 – C16 Alkyl; R2 Hydrogen, C1 – C16 Alkyl, – CF3 Or halogen; R3 Hydrogen, C1 – C16 Alkyl, phenyl, – CF3 , – CN or halogen. The invention provides a simple proceeding from the substrate, the intramolecular C – H arylation reaction, convenient and efficient process for preparing chiral phosphine compound of the new method, for the synthesis of chiral phosphine compound provides a new path. Compared with the prior synthetic method, this method obviously has simplified the reaction step, improves the reaction of atom economy with the reaction efficiency, and a wide range of the substrate. (by machine translation)

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

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PALLADIUM ASSISTED ORGANIC REACTIONS. VI. A NEW METHOD FOR THE PREPARATION OF CYCLOPALLADATED BENZALIMINES

A new, improved method is described for the preparation of cyclopalladated benzalimines; it consists of reacting the ortho-bromobenzalimine with bis(dibenzylideneacetone)palladium(0).A number of substituted o-bromobenzalimines has been studied; the bridged bromide dimers and the corresponding bromo(N-substituted benzalimine-6,C,N)triphenylphosphinepalladium(II) complexes have been fully characterised and 1H and 13C NMR spectral data recorded.In the cases of the N-phenylbenzalimines studied, bis(triphenylphosphine) complexes were also isolated and characterised.

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

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Access to functionalized bicyclo[4,3,0]nonenes via palladium-catalyzed oxidative cyclization of 2-allylcyclohexyl oximes

A new palladium-catalyzed oxidative cyclization process leading to the functionalized bicyclo[4,3,0]nonenes is serendipitously discovered during attempts to form aza-heterocycle by the amino-Heck reaction of trans-2-vinylclohexyl phosphinyloxime. Under the influence of Pd(dba) 2/Et3N/1:1 N2-O2 (1:1, v/v) (Method A) or Pd(OAc)2/Et3N/O2 (Method B), the reactions afford the substituted cis-1-hydroxyl-8-formyl-bicyclo[4,3,0]non-8(9)- enes or bicycle[4,3,0]non-1(9)-en-8-ones in varying yields with the incorporation of molecular oxygen into the structures. The 5,6-bicyclic scaffold of these products is presumably derived from tandem double intramolecular cyclization followed by the ring-opening of an aza-palladium(II) tricyclic intermediate.

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

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Fluoride-Promoted Cross-Coupling Reactions of Alkenylsilanols. Elucidation of the Mechanism through Spectroscopic and Kinetic Analysis

The mechanism of the palladium-catalyzed cross-coupling reaction of (E)-dimethyl-(1-heptenyl)-silanol ((E)-1) and of (E)-diisopropyl-(1-heptenyl)silanol ((E)-2) with 2-iodothiophene has been investigated through spectroscopic and kinetic analysis. A common intermediate in cross-coupling reactions of several types of organosilicon precursors has been identified as a hydrogen-bonded complex between tetrabutyl-ammonium fluoride (TBAF) and a silanol. The order in each component has been determined by plotting the initial rates of the cross-coupling reaction at varying concentrations. These data provide a mechanistic picture that involves a fast and irreversible oxidative insertion of palladium into the aryl iodide and a subsequent turnover-limiting transmetalation step achieved through a fluoride-activated disiloxane derived from the particular silanol employed. The inverse order dependence of TBAF at high concentration is consistent with a pathway that proceeds through a hydrogen-bonded complex which is the lowest energy silicon species in solution.

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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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Triazine compounds as inhibitors of bacterial type III protein secretion systems

In accordance with the present invention, compounds that inhibit Type III protein section have been identified, and methods for their use provided. In one aspect of the invention, compounds useful in the inhibition of Type III protein section and/or in the treatment and prevention of bacterial infections, particularly Gram-negative bacterial infections, are provided. In another aspect of the invention, methods are provided for the inhibition of Type III protein secretion and/or the treatment and prevention of bacterial infections, particularly Gram-negative bacterial infections using the compounds of the invention.

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

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Reaction of haloarenetricarbonylchromium with trimethylphosphite: palladium-catalyzed Arbuzov reaction versus arene displacement by trimethylphosphite

The Arbuzov reaction of trimethylphosphite with p-bromo-, and also with p-chloro-toluenetricarbonylchromium is achieved at 80-120 deg C, in the presence of a Pd0 or PdII complex, which acts as a catalyst.A competitive displacement of the haloarene by trimethylphosphite occurs, and the resulting diastereoisomeric complexes are obtained.

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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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New routes to the synthesis of chloro-carbonyls of palladium(II) and platinum(II)

[Pt(CO)x]n (x?2), the already described species obtained by the reaction of platinum(0) olefin complexes with carbon monoxide, reacts promptly at room temperature with SO2Cl2 under CO affording cis-PtCl2(CO)2. [Pd2(CO)y]n (y?1), obtained by Pd(dba)2 and CO at room temperature, reacts in the same conditions yielding Pd2Cl4(CO)2. Similarly, although more slowly, finely divided platinum and palladium, in the form of metal blacks, react with SO2Cl2 and CO at room temperature producing again cis-PtCl2(CO)2 and Pd2Cl4(CO)2, respectively. In the absence of CO no reaction is observed within 4 weeks.

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

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Isomerizing Methoxycarbonylation of Alkenes to Esters Using a Bis(phosphorinone)xylene Palladium Catalyst

The synthesis and characterization of bulky diphosphine 1,2-bis(4-phosphorinone)xylene, BPX, and its palladium complexes [(BPX)PdCl2] and [(BPX)Pd(O2CCF3)2] are described. BPX was evaluated as a ligand in Pd-catalyzed isomerizing methoxycarbonylation. A broad range of alkenes, including terminal, internal, branched, and functionalized alkenes, can be converted to esters with activities and selectivities matching or surpassing the performance of the state-of-the-art palladium bis(di(tert-butyl)phosphino-o-xylene (Pd-DTBPX) catalyst. A molecular structure of the precatalyst [(BPX)Pd(O2CCF3)2] was obtained showing a square planar geometry and a bite angle of 100.11(3). Rhodium carbonyl complexes [(BPX)Rh(CO)Cl] and [(DTBPX)Rh(CO)Cl] were synthesized to compare the relative electronic parameters, revealing a nu(C?O) of 1956.8 and 1948.3 cm-1, respectively, suggesting a reduced ability of BPX to donate electron density to the metal relative to DTBPX. Competitive protonation experiments between BPX and DTBPX in the presence of CH3SO3H exclusively produce [DTBPX(H)2]2+, providing additional evidence that BPX is a much weaker base than DTBPX. This could be due to either the effect of the electron-withdrawing ketone group in the phosphorinone ring or the compression of the C-P-C bond angle induced by the ring structure. The 31P NMR (CDCl3) chemical shift of BPX is 5.6 ppm, upfield of DTBPX at 27.6 ppm. This anomalous result is attributed to a strong gamma substituent effect of C=O in the BPX ligand. The improved activity of Pd-BPX, relative to Pd-DTBPX, could be attributed to a more electrophilic PdII center, which could accelerate the rate-determining methanolysis step.

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

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The synthesis of, and characterization of the dynamic processes occurring in Pd(ii) chelate complexes of 2-pyridyldiphenylphosphine

Pd(ii) complexes in which 2-pyridyldiphenylphosphine (Ph2Ppy) chelates the Pd(ii) centre have been prepared and characterized by multinuclear NMR spectroscopy and by X-ray crystallographic analysis. trans- [Pd(kappa1-Ph2Ppy)2Cl2] is transformed into [Pd(kappa2-Ph2Ppy)(kappa1- Ph2Ppy)Cl]Cl by the addition of a few drops of methanol to dichloromethane solutions, and into [Pd(kappa2-Ph 2Ppy)(kappa1-Ph2Ppy)Cl]X by addition of AgX or TlX, (X = BF4-, CF3SO3 – or MeSO3-). [Pd(kappa1-Ph 2Ppy)2(p-benzoquinone)] can be transformed into [Pd(kappa2-Ph2Ppy)(kappa1-Ph 2Ppy)(MeSO3)][MeSO3] by the addition of two equivalents of MeSO3H. Addition of further MeSO3H affords [Pd(kappa2-Ph2Ppy)(kappa1-Ph 2PpyH)(MeSO3)][MeSO3]2. Addition of two equivalents of CF3SO3H, MeSO3H or CF 3CO2H and two equivalents of Ph2Ppy to [Pd(OAc)2] in CH2Cl2 or CH2Cl 2-MeOH affords [Pd(kappa2-Ph2Ppy) (kappa1-Ph2Ppy)X]X, (X = CF3SO 3-, MeSO3- or CF3CO 2-), however addition of two equivalents of HBF 4¡¤Et2O affords a different complex, tentatively formulated as [Pd(kappa2-Ph2Ppy)2]X 2. Addition of excess acid results in the clean formation of [Pd(kappa2-Ph2Ppy)(kappa1-Ph 2PpyH)(X)]X2. In methanol, addition of MeSO3H and three equivalents of Ph2Ppy to [Pd(OAc)2] affords [Pd(kappa2-Ph2Ppy)(kappa1-Ph 2Ppy)2][MeSO3]2 as the principal Pd-phosphine complex. The fluxional processes occuring in these complexes and in [Pd (kappa1-Ph2Ppy)3Cl]X, (X = Cl, OTf) and the potential for hemilability of the Ph2Ppy ligand has been investigated by variable-temperature NMR. The activation entropy and enthalpy for the regiospecific fluxional processes occuring in [Pd(kappa2- Ph2Ppy)(kappa1-Ph2Ppy)2][MeSO 3]2 have been determined and are in the range -10 to -30 J mol-1 K-1 and ca. 30 kJ mol-1 respectively, consistent with associative pathways being followed. The observed regioselectivities of the exchanges are attributed to the constraints imposed by microscopic reversibility and the small bite angle of the Ph2Ppy ligand. X-Ray crystal structure determinations of trans-[Pd(kappa1- Ph2Ppy)2Cl2], [Pd(kappa2-Ph 2Ppy)(kappa1-Ph2Ppy)Cl][BF4], [Pd(kappa1-Ph2Ppy)2(p-benzoquinone)], trans-[Pd(kappa1-Ph2PpyH)2Cl 2][MeSO3]2, and [Pd(kappa1-Ph 2Ppy)3Cl](Cl) are reported. In [Pd(kappa2- Ph2Ppy)(kappa1-Ph2Ppy)Cl][BF4] a donor-acceptor interaction is seen between the pyridyl-N of the monodentate Ph2Ppy ligand and the phosphorus of the chelating Ph2Ppy resulting in a trigonal bipyramidal geometry at this phosphorus.

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