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The complexes behave like a monodentate phosphine ligand and displace the labile ligands from , trans- and cis- (dmso = dimethyl sulfoxide) to yield the corresponding dppf-bridged heteropolymetallic complexes of general formula y> (M’ = Au, x = y = 1; M’ = Pd or Pt, x = y = 2).Only the trans isomers have been isolated for PdII and PtII.Isomerisation of the M’ = Pt, M = Cr complex to the cis form, followed by partial elimination of to form , after 3d in CDCl3 was revealed by NMR spectroscopy.The solution characteristics of both geometrical isomers of the representative M’ = Pt, M = Cr complex have been established by two-dimensional NMR studies.UV-Photolytic degradation of the M’ = Pd or Pt, M complexes generally gave , , and .The molecular structures of trans-2> and have been determined.The former represents a trimetallic pentanuclear aggregate and the latter a metalloligand with a pendant phosphine on a bimetallic complex.Cyclic voltammetry of all the complexes has been examined and generally reveals one chemically reversible phosphinoferrocene-based oxidation, followed by an irreversible oxidation of the complex.

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

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omega-(4-Bromophenyl)alkanoic acids 2c-e were obtained from 1-bromo-4-alkenylbenzenes 5c-e by hydroboration-thermal isomerization-oxidation. Their esters 11c-e were transformed in good yields into the corresponding boronates 12c-e by the cross-coupling reaction with (10) in an ionic liquid, [bmim][BF4]. The use of pinacolborane for the coupling reaction in the ionic liquid gave debromination products, and low yields of 12c-e. Ethyl 3-(4-bromophenyl)propanoate (7c) was transformed into ethyl 3-(4-[1,3,2]dioxaborolanyl)propanoate (9c) by the cross-coupling with [2,2?]bi[[1,3,2]dioxaborinanyl].

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Reference:
Chapter 1 An introduction to palladium catalysis,
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Conditions have been developed for the palladium-catalyzed cross-coupling of 3-bromo-2,1-borazaronaphthalenes with potassium alkenyltrifluoroborates. Twenty-seven alkenyl-substituted azaborines have been synthesized through this method, providing access to a family of 2,1-borazaronaphthalenes with alkenyl substitution at the C3 position.

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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 high-yielding, ligand-free, palladium-catalyzed isocyanide insertion reaction for the synthesis of phthalazino[1,2-b]quinazolinones from the readily obtainable quinazolinones has been developed. Easily handled and relatively low-cost palladium(II) acetate was used as the catalyst, without an additional ligand. Preparation of the quinazolinones involved the cascade reaction of isatoic anhydrides, phenylhydrazines and 2-bromobenzaldehyde catalyzed by p-toluenesulfonic acid in one pot. This novel protocol may be applicable for the synthesis of other important ring-fused heterocyclic compounds. Georg Thieme Verlag Stuttgart. New York.

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

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Trans -selective monoarylation of 1,1-dibromo- and 1,1-dichloro-1-alkenes (1) can be achieved in >80% yields and in ?98-99% stereoselectivity with arylzinc bromides in the presence of a catalytic amount of Cl2Pd(DPEphos) or Cl2Pd(dppb), the former permitting cleaner and higher yielding reactions. Although THF is a generally satisfactory solvent, ether and toluene are superior to THF in some cases. The second substitution of (Z)-alpha-bromostyrenes (3) with alkylzincs in the presence of 2 mol% of Pd(t Bu3P)2 proceeds to give the corresponding 2 in >90% yields and in ?98-99% stereoselectivity. Although somewhat less satisfactory, the use of Cl2Pd(DPEphos) permits a one-pot tandem arylation-alkylation.

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

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Palladium-catalysed hydroesterification of trimethylsilylacetylenes 1 gives (E)-beta-ethoxycarbonylvinylsilanes 2 exclusively in excellent yields.

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Chapter 1 An introduction to palladium catalysis,
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The effect of the natural bite angle (betan) of diphosphane ligands on catalyst selectivity and activity in the palladiumcatalyzed cross-coupling of sec-butyl magnesium chloride with bromobenzene was investigated. The calculated natural bite angles range from 78 for dppe (1,2-bisdiphenylphosphanoethane) to 110 for Xantphos. The natural bite angle of diphosphane ligands has a large effect on catalyst selectivity and activity. Both rate and selectivity of the cross-coupling reaction increase with increasing bite angle and reach a maximum value with DPEphos (betan = 102.7 ). Larger bite angles of the diphosphane ligands result in a decreased selectivity and activity.

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Chapter 1 An introduction to palladium catalysis,
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A general synthetic route to inherently luminescent and optically active 6-fold substituted C3-symmetric and asymmetric biphenyl-based trianglimines has been developed. The synthesis of these hexa-substituted triangular macrocycles takes advantage of a convenient method for the synthesis of symmetrically and asymmetrically difunctionalized biphenyl dialdehydes through a convergent two-step aromatic nucleophilic substitution-one-pot Suzuki-coupling reaction protocol. A modular [3+3] diamine-dialdehyde cyclocondensation reaction between both the symmetrically and asymmetrically difunctionalized-4,4?-biphenyldialdehydes with enantiomerically pure (1R,2R)-1,2-diaminocyclohexane was employed to construct the hexa-substituted triangular macrocycles. B97-D/6-311G(2d,p) density functional theory determined structures and X-ray crystallographic analysis reveal that the six substituents appended to the biphenyl legs of the trianglimine macrocycles adopt an alternating conformation not unlike the 1,3,5-alternate conformation observed for calix[6]arenes. Reduction of the imine bonds using NaBH4 afforded the corresponding 6-fold substituted trianglamine without the need to alkylate the amine nitrogen atoms which could hinder their later use as metal coordination sites and without having to introduce asymmetric carbons.

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Chapter 1 An introduction to palladium catalysis,
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A novel bis-platinum(ii) terpyridine-based macrocycle has been quantitatively obtained by self-assembly; the Pt(ii) host binds neutral planar and electron-rich aromatic guests with good selectivity in DMSO. The Royal Society of Chemistry.

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

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Palladium can do it! A novel palladium-catalyzed reaction between the bulky alpha-carbon centers of two ketones has led to the construction of 2,3-diaryl-1,4-diketones by employing alpha-chloroketones as electrophiles and zinc ketone enolates as nucleophiles (see scheme). This reaction allows the synthesis of bulky 1,4-diketones and is complementary with classic nucleophilic substitution reactions. Copyright

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