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

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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

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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

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Novel heterodinuclear organopalladium complexes having an unsymmetrical PN ligand (Et2NC2H4PPh2-kappa2N,P)RPd-MLn (MLn = Co(CO)4; R = Me (2a), Ph (2b), MLn = MoCp(CO)3; R = Ph (3b)) are synthesized by metathetical reactions of PdRX(Et2NC2H4PPh2-kappa2N,P) (X = I, NO3) with Na+[MLn]-. Reversible dissociation of the Pd-N bond in 3b is revealed by variable temperature NMR studies. Reactions of 2a and 2b with CO yield corresponding acyl complexes (Et2NC2H4PPh2-kappa2N,P)(RCO)Pd-Co(CO)4 (R = Me (5a), Ph (5b)). Rate of CO insertion for 2a and 2b is significantly faster than those for mononuclear methylpalladium complex, PdMeI(Et2NC2H4PPh2-kappa2N,P) (1a), and methylpalladium-cobalt complex with a 1,2-bis(diphenylphosphino)ethane (dppe) ligand, (dppe-kappa2P,P?)MePd-Co(CO)4 (6a). 5a smoothly reacts with nucleophiles such as diethylamine, methanol and benzenethiol to give corresponding amide, ester and thioester, respectively. These reactions of 5a are also significantly faster than those of corresponding mononuclear analogues and the similar heterodinuclear complexes with symmetrical bidentate ligands such as 1,2-bis(diphenylphosphino)ethane or N,N,N?,N?-tetramethylethylenediamine 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 insertion of 1,1-difluoroallenes was carried out to form a C-C bond exclusively on their central carbon. o-Bromophenyl-bearing 1,1-difluoroallenes underwent intramolecular insertion in the presence of a palladium catalyst. Regioselective C-C bond formation occurred to form a six-membered carbocycle, leading to pharmaceutically and agrochemically promising difluoromethylated naphthalenes.

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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 palladium-catalyzed thiocarbonylation of styrene derivatives is reported for the first time. The combination of thiols as nucleophiles and a bidentate ligand ensures a unique reaction outcome with high regioselectivity toward the more valuable branched isomer and new reactivity. The ambient reaction conditions (temperature, catalyst loading) and the use of a CO surrogate render this transformation a useful method for the synthesis of thioesters from available feedstock. Various functional groups on arene and thiol substituents are tolerated by the system. Notably, challenging ortho-substituted styrenes are converted with unprecedentedly high regioselectivity.

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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 reaction of Pd(dppf)(Ph)(I) (1, dppf = Ph2PC5H4FeC5H4PPh2) with 1.5 equiv of PPh2H leads to the formation of the Pd(II) dinuclear complex Pd2I2(mu-dppf)(mu-H)(mu-PPh2) (2) and the phosphines PPh3 and dppf. The reaction of 1 with 1 equiv of PCy2H (Cy = cyclo-C6H11) slowly gives Pd2I2(mu-dppf)(mu-H)(mu-PCy2) (3). Complex 2 reacts further with PPh2H to give the known [Pd(mu-PPh2)(I)(PPh2H)]2 (4). Reaction of Pd(dcpm)(Ph)(I) (dcpm = Cy2PCH2PCy2) with PPh2H gives [Pd2(PPh2H)2(mu-dcpm)(mu-PPh2)][I] (5). Treatment of Pd(dmpe)(Me)(Cl) (dmpe = Me2PCH2CH2PMe2) with AgOTf and PPh2H gives [Pd(dmpe)(mu-PPh2)]2[OTf]2 (6, OTf = OSO2CF3) as well as a small amount of [Pd2(dmpe)2(mu-H)(mu-PPh2)][OTf]2 (7). Slow decomposition of [Pd(dmpe)(Me)(PCy2H)]+, prepared by the reaction of Pd(dmpe)(Me)(Cl), AgOTf, and PCy2H, gives [Pd2(dmpe)2(mu-H)(mu-PCy2)][OTf]2 (8), which was also prepared from Pd(dmpe)Cl2, AgOTf, Pd(dmpe)(dba) (dba = dibenzylideneacetone), and PCy2H. Complexes 3, 4, 5, and 8 were structurally characterized by X-ray crystallography.

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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 competitive experiments with cis- and trans-5-t-butyl-2-methylenecyclohexanols and their acetates, stereocontrol in the Pd- and Ni-catalysed alkylation of allylic derivatives and the Mo-catalysed isomerisation of allylic alcohols is observed.

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