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Under anhydrous conditions, 4-phenyl-2H-chromenes were obtained in excellent yields by a cross-coupling reaction of 4-trifluoromethylsulfonyloxy-2H-chromenes with arylboronic acids, except for o-methoxyphenylboronic acid, in the presence of K2CO3 and several palladium catalysts. Although copper(I) iodide, used as a co-catalyst, showed no effect on this reaction, it was confirmed to act in the case of the coupling reaction of 4-trifluoromethylsulfonyloxy-2H-chromene with tributylphenyltin, instead of phenylboronic acid, in the presence of [Pd(PPh3)4].

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

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N,N-disubstituted amines in which the amino nitrogen atom is bound to the carbon atom of an aromatic ring disubstituted in the positions ortho to the carbon atom, are prepared by allowing a primary amine and a compound in which an ortho, ortho-disubstituted aromatic compound carrying a nucleofuge substituent, to react in a basic environment in the presence of a catalytic palladium(0) complex and a ligand, the ratio of palladium complex to ligand being greater than at least 1:1. A typical embodiment involves the reaction of 2-methyl-6-ethylphenyl-trifluoromethylsulfonate and (S)-1-methoxy-2-aminopropane in the presence of bis(dibenzylideneacetone)palladium, tri-tert.-butylphosphine, and sodium tert.-butoxide to yield (S)-N-(1-methoxyprop-2-yl)-2-methyl-6-ethylphenylamine.

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

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Reactions of (eta5-C5H5-xBr x)M(CO)3 (M = Re, Mn; x = 1, 3, 4, 5) and IZn(CH 2)2 Rf8 in the presence of Cl 2PdL2 catalysts give the title complexes (eta5-C5H5-x((CH2) 2Rf8)x)M(CO)3 accompanied in the case of x = 5 by hydride-transfer byproducts. Extremely high fluorophilicities are realized, and the cyclopentadienyl ligands are readily detached (hv) from the manganese complexes.

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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 protocol for the first direct diarylation of 6,7-benzindoles with aryl iodides at the C4 and C5 positions was developed. The key to this strategy was the employment of pivaloyl as the directing group at the C3 position and the blocking effect at the C6 and C7 positions. The reaction proceeded very well, providing a series of diarylated 6,7-benzindoles without prefunctionalization at the reactive sites. Several examples on the unexpected monoarylation of 6,7-benzindoles at the C5 position were also 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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[Pd(dppf)(MeCN)2](OTf)2 [dppf = 1,1?-bis(diphenylphosphino)ferrocene, OTf = triflate] reacts with pyridyl acetic acid (PyAcOH) to yield a dipalladium ring structure, [Pd2(dppf)2(mu-PyOAc)2](OTf)2 (1). The doubly-bridging ligands exhibit basicity at the pendant carboxyl oxygen to attract AgX (X = OTf or CF3CO2) to form [Pd2Ag2(dppf)2(PyOAc)2(OTf)4] (2) and [Pd2Ag2(dppf)2(PyOAc)2(OTf)2(CF3CO2)2] (3), respectively. Complexes 1 and 2 have been crystallographically characterized. Similar spacer-guest affinity is not found in the Pt(II) or isonicotinate analogues.

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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 scope for the immobilization of homogeneous catalysts in supported ionic liquids was explored. Here, a solution of cationic transition metal complexes in the ionic liquid 1-ethyl-3-methylimidazolium trifluoromethanesulfonate was supported on diatomic earth. The catalysts were then tested in the direct addition of 4-isopropylaniline to phenylacetylene (hydroamination). Supported Rh(I), Pd(II) and Zn(II) complexes combined a higher intrinsic catalytic activity relative to the corresponding homogeneous catalysts with a high selectivity.

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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 scope of the Suzuki-cross-coupling reaction of 6-haloimidazo[1,2-a]pyridines is dependent on the availability of the (hetero)arylboronic acids. Thus, with the aim to develop expanded applications of (hetero)arylations of imidazo[1,2-a]pyridines, we investigated the Negishi- and Stille-cross-coupling reactions at the 6-position. Remarkably, attempts to aply the Negishi-cross-coupling conditions to the organozinc derivative prepared from 6-haloimidazo[1,2-a]pyridine via a lithium-zinc exchange led to the 5-phenyl compound 3 in 54 percent yield instead of the desired 6-phenyl-isomer (Scheme 1). In contrast, various commercially available halogenated five- or six-membered-ring heterocycles were efficiently coupled to the 6-(trialkylstannyl)imidazo[1,2-a]pyridine under Stille conditions (Table 2).

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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 have explored the scope of the palladium-catalyzed nucleophilic ring opening methodology. New highly selective and highly active catalysts have been found for the ring opening of oxabenzonorbornadienes. Employing these catalysts, the addition of various alkyl nucleophiles to oxabenzonorbornadiene has been achieved. In addition, reaction of diethylzinc with [3.2.1] oxabicyclic alkenes has been accomplished to yield ring-opened products as well as functionalized alkene addition products.

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

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3,5-Diferrocenylpyridine was synthesised from 3,5-dibromopyridine and ferroceneboronic acid, in respectable yield (48%), using a microwave-enhanced Suzuki cross-coupling reaction. This novel ligand and its palladium(II) dichloride complex have been fully characterised using elemental analysis, HR-ESI-MS, IR, UV and NMR spectroscopy. Additionally, the molecular structures of 3,5-diferrocenylpyridine and [Pd(3,5-diferrocenylpyridine)2Cl 2] were confirmed by X-ray crystallography. A comprehensive study of the electrochemistry of 3-ferrocenylpyridine, 3,5-diferrocenylpyridine and their palladium(II) dichloride complexes was performed using traditional hexafluorophosphate and weakly-coordinating fluorinated aryl borate anions. Electronic communication between the two proximal ferrocenyl centres of 3,5-diferrocenylpyridine and its palladium complex is only observed when the weakly-coordinating fluorinated aryl borate anions are used as the supporting electrolyte.

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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 (+)-tanikolide, a bioactive delta-lactone of marine origin, was successfully accomplished by utilizing a bromoalkene derivative conveniently synthesized from the corresponding 1-acyloxy-2,3-dibromoalkane by the regioselective and mild HBr-elimination reaction, along with the Pd-mediated C-C coupling reaction and the Sharpless asymmetric epoxidation as key steps.

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