New explortion of Bis(dibenzylideneacetone)palladium

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Monodentate Phosphorus Ligand-Enabled General Palladium-Catalyzed Allylic C-H Alkylation of Terminal Alkenes

Monodentate phosphorus ligands have been found to enable the palladium-catalyzed allylic C-H alkylation reaction of terminal alkenes with a wide variety of carbon nucleophiles. Moreover, an asymmetric allylic C-H alkylation of terminal alkenes with pyrazol-5-ones has been established in the presence of chiral phosphoramidite ligand and chiral phosphoric acid as co-catalyst. Mechanistic studies suggest that a ternary Pd(0) complex, coordinated with a monodentate phosphorus ligand, benzoquinone, and alkene, is most likely to be an active species.

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

Brief introduction of Bis(dibenzylideneacetone)palladium

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Palladium-Catalyzed Selective alpha-Alkenylation of Pyridylmethyl Ethers with Vinyl Bromides

An efficient palladium-catalyzed alpha-alkenylation of pyridylmethyl ethers with vinyl bromides is presented. A Pd/NIXANTPHOS-based catalyst system enables a mild and chemoselective coupling between a variety of pyridylmethyl ethers and vinyl bromides in good to excellent yields. Under the mild conditions, beta,gamma-unsaturated products are obtained without isomerization or Heck byproducts observed.

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

The important role of Bis(dibenzylideneacetone)palladium

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Substrate-Controlled Regio- and Stereoselective Synthesis of Boron-Substituted 1,4-Dienes via Copper-Catalyzed Boryl-Allylation of Alkynes with Allyl Phosphates and Bis(pinacolato)diboron

Boron-substituted 1,4-dienes are versatile building blocks for the synthesis of 1,4-dienes (skipped alkenes), a common motif in bioactive natural products, because of their utility in the Suzuki-Miyaura coupling reaction and conjugate additions. A method for the synthesis of boron-substituted 1,4-dienes by means of copper-catalyzed boryl-allylation of alkynes with allyl phosphate and bis(pinacolato)diboron has been developed. The regioselectivity with respect to the alkyne and allyl phosphate depends on the structures of both the alkyne and the allyl phosphate. For alkynes bearing at least one aryl substituent, addition of borylcopper to the alkyne mainly generates a beta-boryl-alpha-aryl-alpha-alkenylcopper species, whose subsequent reaction with secondary allyl phosphates provides gamma-(4E)-selective boron-substituted 1,4-dienes, and with primary allyl phosphates provided alpha-selective boron-substituted 1,4-dienes. On the other hand, the alpha-boryl-alpha-aryl-beta-alkenylcopper species formed as a minor intermediate from aryl alkyl acetylenes and the beta-borylalkenylcopper species formed from dialkyl acetylenes show poor regioselectivity with respect to the secondary allyl phosphate and produce a mixture of alpha- and gamma-selective boron-substituted 1,4-dienes. However, their reactions with the primary allyl phosphate are highly gamma-selective. For all of the alpha-selective reactions, the configuration of the C=C bond of the allyl phosphate was retained in the products. The palladium-catalyzed cross-coupling of boron-substituted 1,4-dienes and aromatic, alkenyl, and alkynyl halides gave polyenes or enynes in 68%-95% yield, demonstrating that these boron-substituted 1,4-dienes are versatile building blocks for the synthesis of 1,4-dienes.

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

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SPIRO-1,1′-BIINDANE-7,7-BISPHOSPHINE OXIDES AS HIGHLY ACTIVE SUPPORTING LIGANDS FOR PALLADIUM-CATALYZED ASYMMETRIC HECK REACTION

The present invention relates to catalyst complexes comprising palladium (Pd) and at least one spiro-1,1 ‘-biindane-7,7’- bisphosphine oxide ligand as disclosed herein, and their use. The present invention is further directed to the asymmetric Pd-catalyzed covalent carbon-carbon single bond formation from aryl, heteroaryl and alkenyl triflates and halides and olefins utilising the said catalyst complexes.

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

Final Thoughts on Chemistry for 53199-31-8

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Activation and deactivation of neutral palladium(II) phosphinesulfonato polymerization catalysts

13C-Labeled ethylene polymerization (pre)catalysts [kappa2-(anisyl)2P,O]Pd(13CH3)(L) (1-13CH3-L) (L = pyridine, dmso) based on di(2-anisyl)phosphine benzenesulfonate were used to assess the degree of incorporation of 13CH3 groups into the formed polyethylenes. Polymerizations of variable reaction time reveal that ca. 60-85% of the 13C-label is found in the polymer after already 1 min polymerization time, which provides evidence that the pre-equilibration between the catalyst precursor 1-13CH3-L and the active species 1-13CH3-(ethylene) is fast with respect to chain growth. The fraction of 1-13CH3-L that initiates chain growth is likely higher than the 60-85% determined from the 13C-labeled polymer chain ends since (a) chain walking results in in-chain incorporation of the 13C-label, (b) irreversible catalyst deactivation by formation of saturated (and partially volatile) alkanes diminishes the amount of 13CH3 groups incorporated into the polymer, and (c) palladium-bound 13CH3 groups, and more general palladium-bound alkyl(polymeryl) chains, partially transfer to phosphorus by reductive elimination. NMR and ESI-MS analyses of thermolysis reactions of 1-13CH3-L provide evidence that a mixture of phosphonium salts (13CH3)xP+(aryl)4-x (2-7) is formed in the absence of ethylene. In addition, isolation and characterization of the mixed bis(chelate) palladium complex [kappa2-(anisyl)2P,O]Pd[kappa2-(anisyl) (13CH3)P,O] (11) by NMR and X-ray diffraction analyses from these mixtures indicate that oxidative addition of phosphonium salts to palladium(0) species is also operative. The scrambling of palladium-bound carbyls and phosphorus-bound aryls is also relevant under NMR, as well as preparative reactor polymerization conditions exemplified by the X-ray diffraction analysis of [kappa2-(anisyl)2P,O] Pd[kappa2-(anisyl)(CH2CH3)P,O] (12) and [kappa2-(anisyl)2P,O]Pd[kappa2-(anisyl) ((CH2)3CH3)P,O] (13) isolated from pressure reactor polymerization experiments. In addition, ESI-MS analyses of reactor polymerization filtrates indicate the presence of (odd- and even-numbered alkyl)(anisyl)phosphine sulfonates (14) and their respective phosphine oxides (15). Furthermore, 2-(vinyl)anisole was detected in NMR tube and reactor polymerizations, which results from ethylene insertion into a palladium-anisyl bond and concomitant beta-hydride elimination. In addition to these scrambling reactions, formation of alkanes or fully saturated polymer chains, bis(chelate)palladium complexes [kappa2-P,O]2Pd, and palladium black was identified as an irreversible catalyst deactivation pathway. This deactivation proceeds by reaction of palladium alkyl complexes with palladium hydride complexes [kappa2-P,O]Pd(H)(L) or by reaction with the free ligand H[P,O] generated by reductive elimination from [kappa2-P,O]Pd(H)(L). The model hydride complex 1-H-P tBu3 has been synthesized in order to establish whether 1-H-PtBu3 or H[P,O] is responsible for the irreversible catalyst deactivation. However, upon reaction with 1-(13)CH 3-L or 1-CH2CH3-PPh3, both 1-H-PtBu3 and H[P,O] result in formation of methane or ethane, even though H[P,O] reacts faster than 1-H-PtBu3. DFT calculations show that reductive elimination to form H[P,O] and (alkyl)[P,O] from 1-H/(alkyl)-PtBu3 is kinetically accessible, as is the oxidative readdition of the P-H bond of H[P,O] and the P-anisyl bond of (alkyl)[P,O] to [Pd(PtBu3)2]. These calculations also indicate that for a reaction sequence comprising reductive elimination of H[P,O] from 1-H-PtBu3 and reaction of H[P,O] with 1-CH3-PtBu3, 1-CH3-dmso, or 1-CH2CH3-PPh3 to form methane or ethane, the rate-limiting step is reductive elimination of H[P,O] with a barrier of 124 kJ mol-1. However, a second reaction coordinate was found for the reaction of 1-H-PtBu3 with 1-CH3-P tBu3 or 1-CH3-dmso, which evolves into bimetallic transition-state geometries with a nearly linear H-(CH 3)-Pd alignment and which exhibits a barrier of 131 or 95 kJ mol -1 for the formation of methane.

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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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Synthesis and structural characterisation of [Pd2(mu-Br)2(PBut3)2], an example of a palladium(I)-palladium(I) dimer

The syntheses, spectroscopic characterisation and in one case (X = Br) the single-crystal structure of the novel PdI-PdI dimers [Pd2(mu-X)2(PBut3)2] (X = Br or I) have been determined; preliminary results on their reactions with CO, H2, CNC6H3Me2 and C2H2 have also been obtained.

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

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Aligning Potency and Pharmacokinetic Properties for Pyridine-Based NCINIs

Optimization of pyridine-based noncatalytic site integrase inhibitors (NCINIs) based on compound 2 has led to the discovery of molecules capable of inhibiting virus harboring N124 variants of HIV integrase (IN) while maintaining minimal contribution of enterohepatic recirculation to clearance in rat. Structure-activity relationships at the C6 position established chemical space where the extent of enterohepatic recirculation in the rat is minimized. Desymmetrization of the C4 substituent allowed for potency optimization against virus having the N124 variant of integrase. Combination of these lessons led to the discovery of compound 20, having balanced serum-shifted antiviral potency and minimized excretion in to the biliary tract in rat, potentially representing a clinically viable starting point for a new treatment option for individuals infected with HIV.

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

Discovery of Bis(tri-tert-butylphosphine)palladium

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Toward an Improved Understanding of the Unusual Reactivity of Pd 0/Trialkylphosphane Catalysts in Cross-Couplings of Alkyl Electrophiles: Quantifying the Factors That Determine the Rate of Oxidative Addition

What a difference a ligand makes! The reactivity of Pd 0/trialkylphosphane complexes is of great interest because of their unusual effectiveness as cross-coupling catalysts for alkyl electrophiles [Eq. (1)]. This study sheds light on various aspects of the critical oxidative-addition step of the catalytic cycle.

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

Archives for Chemistry Experiments of 53199-31-8

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The expedient synthesis of 4,2?-difluoro-5?-(7- trifluoromethylimidazo[1,2-a]pyrimidin-3-yl)biphenyl-2-carbonitrile, a GABA alpha2/3 agonist

An expedient regioselective synthesis of a GABA alpha2/3 agonist 1 is described. The key step is an efficient regioselective palladium-catalyzed coupling of 7-trifluoromethylimidazo[1,2-a]pyrimidine (5) to 5?-chloro-4,2?-difluorobiphenyl-2-carbonitrile (15). The efficiency of this step was affected by the choice of solvent, ligand, and tetrabutylammonium salt additive.

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

More research is needed about Bis(dibenzylideneacetone)palladium

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A new tripod PPN bridging ligand and its copper, silver and palladium complexes: Syntheses, characterizations and X-ray structures

A new tripod bridging ligand 2-{bis(diisopropylphosphino)methyl}-1-methylimidazole, MeImCH(Pi-Pr2)2 (PPN) was synthesized conveniently by reacting 2-{bis(trimethylsilyl)methyl}-1- methylimidazole and chlorodiisopropylphosphine. The dicationic dinuclear complex [Cu2(PPN)2][CIO4]2 (1) was prepared by the reaction of the ligand with [Cu(MeCN)4]ClO4 in acetonitrile. The reaction of the ligand with AgNO3 in propane-2-ol followed by addition of NH4PF6 led to the formation of a similar type complex [Ag2(PPN)2][PF6]2 (2). The X-ray diffraction studies of 1 and 2 revealed a mu2-eta1:eta2 tripod-like bonding of the PPN ligand, with one P and one N atom chelating to one metal ion and the remaining one P atom binds to another metal ion, affording a face-to-face type molecule. An eight-membered M2P4C2 and a 10-membered M2P2N2C4 ring are thus formed with this new functional diphosphine ligand. In both complexes the two metal ions are held in very close proximity [2.6707 A? for 1 and 2.859(3) A? for 2]. Coplex 1 underwent a rapid ligand exchange process in solution. Besides these dinuclear complexes the ligand also afforded a mononuclear palladium complex, [PdCl2(PPN)] (3), when it was treated with an equimolar amount of [PdCl2(PhCN)2] in benzene. In 3 the ligand acts as a bidentate chelate through its two phosphorus atoms, leaving the imidazole donor dangling. On the other hand, a P,P-bridged dinuclear Pd(I) complex [Pd2Cl2(PPN)2] (4) was achieved by reacting two moles of the ligand with one mole of [PdCl2(PhCN)2], followed by the addition of one mole of Pd(dba)2 [dba = dibenzylideneacetone].

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