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The development of new methodologies that enable chemo- and stereoselective construction of fluorinated substituents, such as the trifluoromethyl (CF3) group, plays an essential role in the synthesis of new pharmaceutical agents. The exceptional ability of the CF3 moiety to prevent in vivo metabolism as well as improve other pharmacological properties has led to numerous innovative strategies for installing this unique functional group. One potential yet underdeveloped approach to access these trifluoromethylated products is direct substitution of alpha-trifluoromethyl carbanions. Although the electron-withdrawing nature of the CF3 group should facilitate deprotonation of adjacent hydrogens, the propensity of the resulting carbanions to undergo alpha-elimination of fluoride renders this process highly challenging. Herein, we describe a new strategy for stabilizing and utilizing transient alpha-trifluoromethyl carbanions that relies on a neighbouring cationic pi-allyl palladium complex. These palladium-stabilized zwitterions participate in asymmetric [3 + 2] cycloadditions with a broad range of acceptors, generating valuable di- and trifluoromethylated cyclopentanes, pyrrolidines and tetrahydrofurans.

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

Some scientific research about Pd2(DBA)3

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A photoredox/palladium-cocatalyzed enantioselective alkylation of racemic secondary carbonates with 4-alkyl-1,4-dihydropyridines under visible light irradiation has been developed. The present study provides a method for the preparation of optically active diarylalkanes from racemic diarylmethyl carbonates by a dynamic kinetic asymmetric transformation (DYKAT). This photoredox/palladium dual catalysis strategy expands the scope of the asymmetric Pd-catalyzed benzylic substitution reaction and serves as its potential alternative and complement.

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

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An optimized catalyst system of [Pd2(dba)3] and AsPh3 efficiently catalyzes the Stille reaction between a diverse set of functionalized stannanes and halogenated mono-, di- and oligonucleotides. The methodology allows for the facile conjugation of short and long nucleic acid molecules with moieties that are not compatible with conventional chemical or enzymatic synthesis, among them acid-, base-, or fluoride-labile protecting groups, fluorogenic and synthetically challenging moieties with good to near-quantitative yields. Notably, even azides can be directly introduced into oligonucleotides and (deoxy)nucleoside triphosphates, thereby giving direct access to “clickable” nucleic acids.

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

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32005-36-0, Name is Bis(dibenzylideneacetone)palladium, belongs to catalyst-palladium compound, is a common compound. Computed Properties of C34H28O2PdIn an article, once mentioned the new application about 32005-36-0.

Highly effective Pd-catalyzed Heck-type oxidative couplings between arylboronic acids and terminal olefins were reported. It is noteworthy that such reactions could be carried out in the absence of the base and the 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 new palladium and platinum complexes with 3-hydroxypicolinic acid (HpicOH) [M(PPh3)2Cl(picOH)]·CHCl3, [M(bipy)(picOH)]Cl [M = Pd(II) or Pt(II)], K[PdCl(picOH)2] and [Pt(picOH)2] and the new rhenium complexes [ReOI2(PPh3)(picOH)] and [ReO(PPh3)(picOH)2]I have been prepared. The crystal structures of [M(PPh3)2Cl(picOH)]·CHCl3 [M = Pd(II) 1 or Pt(II) 2] and [ReOI2(PPh3)(picOH)] 3 were determined by X-ray diffraction. Complex 3 exhibits a distorted octahedral geometry with the picOH- ligand showing N,O-chelation with a small bite angle O-Re-N of 74.8(3). In complexes 1 and 2 the metal centre is surrounded by a NP2Cl donor set in a distorted square planar arrangement. Therefore, the picOH- ligand is bound through the nitrogen atom, but the distances found between the metal and the carboxylate oxygen [Pd···O(71) 2.773(5) A or Pt···O(71) 2.734(4) A] suggest a [4 + 1] coordination consistent with N,O-chelation for palladium and platinum centres. Infrared, Raman, 1H and 13C-{1H} NMR spectroscopic data for the complexes are consistent with the crystallographic results. In the solid state the complex units of 1 and 3 are aggregated in centrosymmetric dimers based on C-H···Cl or C-H···O hydrogen bonding interactions between the chlorine of the Pd-Cl bond (in 1) or the phenolic oxygen of the picOH- anion (in 3) and a hydrogen atom of a phenyl group of a PPh3 ligand.

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

Extracurricular laboratory:new discovery of [1,1′-Bis(diphenylphosphino)ferrocene]dichloropalladium(II)

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An efficient method for the synthesis of 6-alkyl or 6-aryl purines (nucleosides) was developed via nickel-catalyzed Negishi cross-couplings of 6-chloropurines and organozinc halides. The ligand-free process gave good to excellent isolated yields at room temperature.

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

Extended knowledge of Pd2(DBA)3

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The indium-mediated allylation of novel 3-(2-Boc-hydrazono)indolin-2-one derivatives, followed by a palladium-catalysed carboamination reaction, is described to afford unprecedented spirocyclic oxindoles in good yields. The method provides an efficient access to both cis and trans diastereoisomers of highly functionalized compounds, bearing an N-Boc, 5-substituted pyrazolidine ring at the C3-oxindole spiro junction. The versatility of the method is fully demonstrated starting from a series of substituted isatins and employing a variety of aryl halides in the key cyclization step.

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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 report here an unprecedented palladium-catalysed O-allylation of alpha-hydroxyphosphonates. The method was eventually included in a sequential Pudovik/Tsuji-Trost type O-allylation/Ring-Closing Metathesis to afford a variety of phosphorylated heterocycles of various sizes ranging from 5 to 16 starting from readily available aldehydes. (Figure presented.).

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

Extended knowledge of Tris(dibenzylideneacetone)dipalladium-chloroform

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We found that the hydrazone-Pd-catalyzed direct intermolecular reaction of o-alkynylphenols with allylic acetates afforded the corresponding 2-substituted-3-allylbenzofuran derivatives. This reaction proceeded smoothly at room temperature using a hydrazone-Pd catalyst system.

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

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Total synthesis of structurally complex marine oxacyclic natural products, (-)-gambierol, (-)-brevenal, and (+)-neopeltolide, has been accomplished by exploiting SuzukiMiyaura coupling of enol phosphates, paving the way for biological investigations on these scarcely available substances.

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