Archives for Chemistry Experiments of 1,1′-Bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex

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Nickel and palladium complexes with the 1,1′-bis(diphenylphosphino)ferrocene ligand effectively catalyze regioselective cross-coupling of allylic ethers such as 1- or 3-methyl-2-propenyl silyl ethers with aryl-Grinard reagents, where the nickel catalyst leads to carbon-carbon bond formation at the more substituted posiiton while carbon-carbon bond formation occurs at the less substituted position in the case of the palladium catalyst.Allylation of cis- and trans-5-methyl-2-cyclohexenyl silyl ethers was found to proceed with inversion of configuration with both the nickel and palladium catalysts.The stoichiometric reaction of a (1-methyl-?-allyl)palladium complex with the phenyl-Grinard reagent in the presence of phosphine ligands was also studied.A mechanism involving formation of the ?-allyl(aryl)ML2 intermediate is proposed.

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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 application of sterically hindered palladium catalysts to the regioselective hydrodebromination of 2,3,5-tribromothiophene has been studied in detail, including the effects of catalyst choice, solvent, reaction time, and temperature, as well as the method of NaBH4 addition and the role of chelating additives to effect NaBH4 solubility. Ultimately it was determined that the background reaction between NaBH4 and bromothiophenes is too facile to allow both total conversion and high selectivity. Optimized conditions finally allowed a selectivity of ca. 16:1 with overall conversion of 100%. However, complications of overdebromination under these conditions still limit the yield of the desired 2,3-dibromothiophene to 65%.

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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 first catalytic lactonization of unactivated aryl C-H bonds with CO2 to afford important phthalides is reported. Notably, this method features high selectivity, excellent functional group tolerance, smooth scalability, and facile product diversification. DFT calculations reveal that a novel insertion of two CO2 into the O-Pd bond of a palladacycle might be the key step, providing great potential and a different perspective for carbonylation with CO2.

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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 invention provides novel ligands for transition metal complexes which exhibit high coordination power with respect to metals by being free of substituents at the positions ortho to phosphorus or arsenic and which have electron-withdrawing power comparable to the highest level known in conventional ligands. A ligand of the invention includes a compound represented by General Formula (1): R1R2R3A or General Formula (2): R1R2A-Y-AR3R4 and having a total of 15 to 110 carbon atoms. In the formulae, A is phosphorus or arsenic; R1, R2, R3 and R4 are each independently a substituted pyridyl group having optionally different electron-withdrawing groups bonded to the positions meta to the atom A as well as hydrogen atoms bonded to the positions ortho to the atom A; and Y is a divalent group derived from a C2-20, optionally substituted and optionally heteroatom-containing, aliphatic, alicyclic or aromatic compound or from ferrocene.

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

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Functionalised cyclic enol ethers can be recovered with high levels of enantiocontrol after an asymmetric catalytic [1,3]-rearrangement reaction. These compounds can be further elaborated to a series of carbo- and heterocyclic products in good yield and with excellent levels of stereocontrol.

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

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Readily synthesised and functionalised di-1,4-substituted-1,2,3-triazole “click” ligands are shown to self-assemble into coordinatively saturated, quadruply stranded helicate molecular cages with Pd(ii) ions.

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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 compounds HM(CO)4SnPh3, M = Os (10), Ru (11) are activated in the presence of Pt-(PBut3)2 and Pd(PBut3)2 toward the insertion of PhC 2H into the M-H bond. The compounds PtOs(CO)4-(SnPh 3)(PBut3)[mu-HCC(H)Ph], 12, and PtOs(CO) 4(SnPh3)(PBut3)[mu-H 2CCPh], 13, were obtained from the reaction of 10 with PhC 2H in the presence of Pt(PBut3)2. Compounds 12 and 13 are isomers containing alkenyl ligands formed by the insertion of the PhC2H molecule into the Os-H bond at both the substituted and unsubstituted carbon atoms of the alkyne. Both compounds contain a Pt(PBut3) group that is bonded to the osmium atom and a bridging alkenyl ligand that is pi-bonded to the osmium atom. The reaction of 11 with PhC2H in the presence of Pt(PBut 3)2 yielded the products PtRu(CO)4(SnPh 3)(PBut3)[mu-HC2(H)Ph], 14, and PtRu(CO)4(SnPh3)(PBut3)[mu-H 2C2Ph], 15, which are also isomers similar to 12 and 13. The reaction of 11 with PhC2H in the presence of Pd(PBu t3)2 yielded the product PdRu(CO) 4(SnPh3)(PBut3)[mu-H 2C2Ph], 16. Compound 16 contains a Pd(PBut 3) group bonded to the ruthenium atom and a bridging H 2C2Ph ligand that is pi-bonded to the palladium atom. Compound 10 reacted with Pt(PBut3)2 in the absence of PhC2H to yield the compound PtOs(CO)4(SnPh 3)(PBut3)(mu-H), 17. Compound 17 is a Pt(PBut3) adduct of 10. It contains a Pt-Os bond with a bridging hydrido ligand. Compound 17 reacted with PhC2H to yield 12. Compound 12 reacted with PhC2H to yield the compound PtOs(CO) 3(SnPh3)(PBut3)[mu-HCC(Ph)C(H)C(H) Ph], 18. Compound 18 contains a bridging 2,4-diphenylbutadienyl ligand, HCC(Ph)C(H)C(H)Ph, that is pi-bonded to the osmium atom and sigma-bonded to the platinum atom. Fenkse-Hall molecular orbitals of 17 were calculated. The LUMO of 17 exhibits an empty orbital on the platinum atom that appears to be the most likely site for PhC2H addition prior to its insertion into the Os-H bond.

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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 breast cancer, estrogen receptor alpha (ERalpha) positive cancer accounts for approximately 74% of all diagnoses, and in these settings, it is a primary driver of cell proliferation. Treatment of ERalpha positive breast cancer has long relied on endocrine therapies such as selective estrogen receptor modulators, aromatase inhibitors, and selective estrogen receptor degraders (SERDs). The steroid-based anti-estrogen fulvestrant (5), the only approved SERD, is effective in patients who have not previously been treated with endocrine therapy as well as in patients who have progressed after receiving other endocrine therapies. Its efficacy, however, may be limited due to its poor physicochemical properties. We describe the design and synthesis of a series of potent benzothiophene-containing compounds that exhibit oral bioavailability and preclinical activity as SERDs. This article culminates in the identification of LSZ102 (10), a compound in clinical development for the treatment of ERalpha positive breast cancer.

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

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A new strategy was developed for intercepting the palladium-alkyl species generated in Heck reaction via nucleophilic addition prior to the step of migratory insertion, which leads to a new palladium-catalyzed difunctionalization of enol ethers with aminals and alcohols to afford amino acetals. Mechanistic studies suggested that the cationic cyclometalated Pd(II) complex generated by the oxidative addition of aminal to a Pd(0) species was crucial for this unusual transformation.

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Reference:
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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Abstract: This work reports the synthesis and catalytic properties of new mono- and bidentate palladium(0)-[60]fullerene complexes, prepared by reaction of alpha-keto stabilized phosphorus ylides [Ph2P(CH2)nPPh2=C(H)C(O)C6H4-p-R] (n = 1, R = Ph, NO2, (Y1, Y2); n = 2, R = Ph, NO2, (Y3, Y4)), C60 and Pd(dba)2 (dibenzylideneacetone (dba)). Two coordination modes were observed: bidentate P,C-coordinated in the case of [(eta ?C60)Pd(kappa2 ?Y1)] (1) and [(eta2?C60)Pd(kappa2?Y2)] (2) and monodentate P-coordinated for [(eta2?C60)Pd(Y3)2] (3) and [(eta2?C60)Pd(Y4)2] (4) complexes. All complexes have been fully characterized by 1H, 13C and 31P NMR spectroscopic methods and other conventional techniques such as IR, thermogravimetry, inductively coupled plasma optical emission spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy and transmission electron microscopy analysis. Also, the catalytic activity of [60]fullerene-based nanocatalyst 2 in homo- and heterogeneous Mizoroki?Heck coupling reactions of various aryl chlorides with styrene was evaluated. The results implied that the both reactions exhibit their beneficial aspects such as high activity for homogeneous catalysis and facile separation and reusability for heterogeneous one. Furthermore, DFT studies of geometry-optimized monodentate and bidentate structures for 1 and 3 were calculated at the BP86/LANL2DZ and B3LYP/LANL2MB levels of theory to understand the origin of the observed coordination modes. Graphical Abstract: [Figure not available: see fulltext.].

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