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A new approach to the total synthesis of anthracycline natural products, nogalamycin and menogaril, was explored. The goal was to enable late-stage introduction of the EF-ring segment. The new synthetic route has been developed through strategic application of a Suzuki-Miyaura reaction as the key step, which coupled the EF-ring segment with the D-ring to give a 1,1?-disubsitituted alkene in good yield under biphasic conditions. Further manipulation of the coupling product completed the construction of the DEF-ring 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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An efficient method for synthesis of 6-alkynyl-substituted androstane derivatives was developed via the Pd-catalyzed Sonogashira-Hagihara coupling reaction. The use of AgCl as the cocatalyst (instead of traditionally used CuI) was shown to increase the activity of the catalytic system in several cases.

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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 detailed analysis of the optical and photophysical properties of 2,7-bis(phenylene)-9,9-dioctylfluorene (PFP), 2,7-bis(biphenylene)-9,9-dioctylfluorene (BPFBP), 2,7-bis(2-thienyl)-9,9-dioctylfluorene (TFT), and 2,7-bis(2,2-bithien-5-yl)-9,9-dioctylfluorene (BTFBT) in various environments are reported. The optical properties of the free molecules isolated in an alkane matrix are obtained and discussed in terms of the conformation adopted by each derivative in the electronic ground and first excited states. Also, conformational changes are responsible for the optical changes observed at high concentrations in an isopentane glass at 77 K. High quantum yields of all the oligofluorenes at 77 K indicate the absence of quenching effects such as excitonic or aggregation effects. The similar spectral and photophysical properties in matrix and glass environments are explained by the disorder introduced in oligofluorenes by long octyl chains at the C-9 position of the fluorene moiety. To study the effect of intermolecular interactions in the solid state, we recorded the spectra of thin films of these derivatives. The much red-shifted emission band in the solid state cannot be explained by conformational changes and has its origin in the I¿-stacking of conjugated oligomers in their relaxed Si state. As an evidence to show the importance of the role played by octyl chains at the C-9 position of the fluorene moiety, we synthesized two new model compounds: one, without octyl chains at the C-9 position of the fluorene moiety, 2,7-bis(2-thienyl)fluorene (TFTWC) and another with more octyl chains, 1,4-bis(9,9-dioctylfluoren-2-yl)phenyl (FPF). The spectral properties of these derivatives have been studied at room temperature and at 77 K. These systems serve as excellent examples to show the effect of intermolecular interactions on optical properties of oligofluorenes.

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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 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,
Palladium/carbon catalyst regeneration and mechanical application method

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

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