Archives for Chemistry Experiments of Tris(dibenzylideneacetone)dipalladium-chloroform

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Pd-catalyzed [3 + 2] cycloaddition of vinylcyclopropanes with 1-azadienes: synthesis of 4-cyclopentylbenzo[e][1,2,3]oxathiazine 2,2-dioxides

The palladium-catalyzed [3 + 2] cycloaddition of vinylcyclopropanes and 1-azadienes has been developed under mild reaction conditions, giving the multisubstituted cyclopentane derivatives in good to excellent yields with moderate to good diastereoselectivities. The relative configuration of both diastereomers of the products have been determined through X-ray crystallographic diffraction.

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

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Atom economy. Palladium-catalyzed formation of coumarins by addition of phenols and alkynoates via a net C-H insertion

A strategy to achieve ortho substitution of phenols initiated by an ortho-palladation to create coumarins was examined. Indeed, treatment of alkynoates with electron-rich phenols in the presence of a palladium catalyst and an acid does generate coumarins. The scope of the reaction with respect to the phenol and the alkynoates is defined. With unsymmetrical aromatic substrates, generally good regioselectivity that reflects the HOMO coefficients can be observed. In the course of these studies, numerous important naturally occurring coumarins have been synthesized, including fraxinol methyl ether, ayapin, herniarin, xanthoxyletin, and alloxanthoxyletin. The fact that a Pd(0) is the precatalyst rather than a Pd(+2) species and that an acid that reduces Pd(+2) salts, formic acid, functions better than other carboxylic acids raises doubts about the initial working hypothesis. A novel mechanism involving a palladium phenoxide formed from a hydridopalladium carboxylate and phenol is invoked to rationalize the results.

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

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Pd-Catalyzed asymmetric decarboxylative cycloaddition of vinylethylene carbonates with 3-cyanochromones

An efficient method for the construction of furanobenzodihydropyran skeletons has been developed through Pd-catalyzed asymmetric decarboxylative cycloaddition of vinylethylene carbonates with 3-cyanochromones. By using a palladium complex generated in situ from [Pd2(dba)3]·CHCl3 and phosphoramidite L3 as a catalyst under mild reaction conditions, the process afforded furanobenzodihydropyrans bearing vicinal quaternary stereocenters in high yields with good to high enantio- and diastereoselectivities.

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

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Efficient synthesis of seven-membered cyclic ethers using pd(II) catalyst

We report a palladium(II)-catalyzed intramolecular cyclization of oct-2-ene-1,8-diol derivatives to afford seven-membered cyclic ethers without the need for high dilution and without dimer formation.

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

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One of the major reasons for studying chemical kinetics is to use measurements of the macroscopic properties of a system, category: catalyst-palladium, such as the rate of change in the concentration of reactants or products with time.In a article, mentioned the application of 52522-40-4, Name is Tris(dibenzylideneacetone)dipalladium-chloroform, molecular formula is C52H43Cl3O3Pd2

A focused fragment library targeting the antibiotic resistance enzyme – Oxacillinase-48: Synthesis, structural evaluation and inhibitor design

beta-Lactam antibiotics are of utmost importance when treating bacterial infections in the medical community. However, currently their utility is threatened by the emergence and spread of beta-lactam resistance. The most prevalent resistance mechanism to beta-lactam antibiotics is expression of beta-lactamase enzymes. One way to overcome resistance caused by beta-lactamases, is the development of beta-lactamase inhibitors and today several beta-lactamase inhibitors e.g. avibactam, are approved in the clinic. Our focus is the oxacillinase-48 (OXA-48), an enzyme reported to spread rapidly across the world and commonly identified in Escherichia coli and Klebsiella pneumoniae. To guide inhibitor design, we used diversely substituted 3-aryl and 3-heteroaryl benzoic acids to probe the active site of OXA-48 for useful enzyme-inhibitor interactions. In the presented study, a focused fragment library containing 49 3-substituted benzoic acid derivatives were synthesised and biochemically characterized. Based on crystallographic data from 33 fragment-enzyme complexes, the fragments could be classified into R1 or R2 binders by their overall binding conformation in relation to the binding of the R1 and R2 side groups of imipenem. Moreover, binding interactions attractive for future inhibitor design were found and their usefulness explored by the rational design and evaluation of merged inhibitors from orthogonally binding fragments. The best inhibitors among the resulting 3,5-disubstituted benzoic acids showed inhibitory potential in the low micromolar range (IC50 = 2.9 muM). For these inhibitors, the complex X-ray structures revealed non-covalent binding to Arg250, Arg214 and Tyr211 in the active site and the interactions observed with the mono-substituted fragments were also identified in the merged structures.

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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 homogeneous catalysis, the catalyst is in the same phase as the reactant. The number of collisions between reactants and catalyst is at a maximum.In a patent, 52522-40-4, name is Tris(dibenzylideneacetone)dipalladium-chloroform, introducing its new discovery. Recommanded Product: Tris(dibenzylideneacetone)dipalladium-chloroform

Operando Spectroscopic and Kinetic Characterization of Aerobic Allylic C-H Acetoxylation Catalyzed by Pd(OAc)2/4,5-Diazafluoren-9-one

Allylic C-H acetoxylations are among the most widely studied palladium(II)-catalyzed C-H oxidation reactions. While the principal reaction steps are well established, key features of the catalytic mechanisms are poorly characterized, including the identity of the turnover-limiting step and the catalyst resting state. Here, we report a mechanistic study of aerobic allylic acetoxylation of allylbenzene with a catalyst system composed of Pd(OAc)2 and 4,5-diazafluoren-9-one (DAF). The DAF ligand is unique in its ability to support aerobic catalytic turnover, even in the absence of benzoquinone or other co-catalysts. Herein, we describe operando spectroscopic analysis of the catalytic reaction using X-ray absorption and NMR spectroscopic methods that allow direct observation of the formation and decay of a palladium(I) species during the reaction. Kinetic studies reveal the presence of two distinct kinetic phases: (1) a burst phase, involving rapid formation of the allylic acetoxylation product and formation of the dimeric PdI complex [PdI(DAF)(OAc)]2, followed by (2) a post-burst phase that coincides with evolution of the catalyst resting state from the PdI dimer into a pi-allyl-PdII species. The data provide unprecedented insights into the role of ancillary ligands in supporting catalytic turnover with O2 as the stoichiometric oxidant and establish an important foundation for the development of improved catalysts for allylic oxidation reactions.

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

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Synthesis and decomposition behavior of a C2-symmetrical palladium(IV) Spirocyclic complex

A novel palladium(IV) complex consisting of a C2-symmetrical palladaspirocycle framework and an ether ligand was assembled only in a single step from commercially available Pd2(dba)3, tetrachloro-1,2-benzoquinone (o-chloranil), and norbornene. The solid-state structure was confirmed by X-ray analysis of a THF complex. The ligand exchange from diethyl ether to pyridine converted the trigonal-bipyramidal complex to a distorted-octahedral bis(pyridine) complex. Similar palladium(IV) spirocyclic complexes were also formed from the reaction of Pd2(dba)3 with o-chloranil and benzonorbornadiene. The benzonorbornadiene-derived complexes exhibited pronounced stability in both the solid state and solution. The complete decomposition of the mono(pyridine) complex required several hours in C6D6 at 70C, and the addition of extra pyridine retarded the decomposition rate. Benzonorbornadiene was obtained as the main organic product, together with two isomeric adducts between o-chloranil and benzonorbornadiene. On the other hand, the decomposition of the pyridine complex took place within 15 min even at -40 to -50C, upon exposure to HCl in a CDCl3 solution.

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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 devised and synthesized a series of electron-rich compounds featuring diphenylamine, carbazole or dibenzo[c,g]carbazole connected via phenylacetylene linkers to an aromatic central unit. The key synthetic step was a high yielding cross coupling reaction between halogenated (bi)naphthalene and organometallic reagents prepared in situ from terminal alkynes (side-arms). By masking one of the iodo functions with a diethyltriazenyl group in the side-arm precursors, we efficiently circumvented the formation of doubly aminated by-products. Although one step longer, this approach led to higher yields of terminal alkynes than the direct coupling route. Spectroscopic and electrochemical measurements supported by computational evidence revealed that conjugation in the 1,4-disubstituted naphthalene backbone is superior to the 1,5 or 2,6 substituted cores. The diphenylamine derivative gets oxidized more readily when compared to its carbazole analogs. Expanding the core to binaphthalene did not alter electronic properties, but influenced the physical characteristics significantly.

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

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Palladium-catalyzed asymmetric [3+2] cycloaddition of 3-diazooxindoles with 2-vinylspiro[cyclopropane-1,2?-indene]-1?,3?-dione proceeded smoothly in the presence of chiral imidazoline-phosphine ligands to give the corresponding highly functionalized spiropyrazolidine derivatives in good to excellent yields (52-99%) along with good enantioselectivities (48-82% ee) under mild conditions.

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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 reactivity of the bifunctionalized ligand NC(Br)N-I 1 [IC6H2(CH2NMe2)2- 3,5-Br-4] has been studied as a versatile synthon for organic and/or organometallic synthesis. Chemoselective metalation (M = Pd, Pt, Li) at the Caryl-I or Caryl-Br bonds was achieved by choosing the appropriate metal precursors. In this way a series of Pt11 and Pd11 complexes were prepared that have a second functional group available for further reactions. These Pt11 and Pd11 complexes were subjected to a wide range of organic and organometallic reactions, revealing the remarkable stability of their M-C sigma-bond and opening an easy route for the synthesis of mono- and (hetero)bimetallic building blocks. The scope of the chemistry of such building blocks shows that they are good candidates for use in the synthesis of dendrimers, bioorganometallic systems, or polymetallic materials. The X-ray crystal structures of the most representative complexes (2, 3a, 19, 20, and 24) are also reported.

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