Stereoisomerically controlled inorganic architectures: synthesis of enantio- and diastereo-merically pure ruthenium–palladium molecular rods from enantiopure building blocks

Wärnmark, Kenneth; Thomas, Jim A.; Heyke, O.; Lehn, Jean‐Marie

doi:10.1039/cc9960000701

Cited by 85 publications

(64 citation statements)

References 21 publications

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“…Synthesis of the diamino-substituted dppz derivative 20a was originally reported by Lehn et al in a Short Communication. [18] Reaction of phendione with freshly prepared 1,2,4,5-tetraaminobenzene in refluxing THF gave the desired diamine, but also the dicondensation product 9,11,20,22-tetraazatetrapyrido[3,2-a:2Ј,3Ј-c:3ЈЈ,2ЈЈ-l:2ЈЈЈ,3ЈЈЈ-n]-pentacene that could not be separated from the diaminosubstituted dppz derivative. A good idea suggested by Torres-Garcia [19] was that the tetraaminobenzene could be neutralized using a strongly acidic cation exchange resin (Amberlyst 15 ® ).…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Amino‐ and Bis(bromomethyl)‐Substitued Bi‐ and TetradentateN‐Heteroaromatic Ligands: Building Blocks for Pyrazino‐Functionalized Fullerene Dyads

Kleineweischede¹,

Mattay²

2006

Eur J Org Chem

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In this paper we describe the synthesis of amino-and bis(bromomethyl)-substituted derivatives of phenanthroline (phen),These substituted bi-and tetradentate N-heteroaromatic ligands are potential synthons for the preparation of the fullerene ligands 4-9. The diketones, 1,10-phenanthroline-5,6-dione 11a (phendione), 2,2-pyridyl 11b and 1,4-dibromo-2,3-butanedione 33 were used as starting materials. Phendione was converted into the phendiamine 13 by a two-step synthesis via the dioxime of the diketone 11a. Amino-substituted dppz and dpq derivatives were obtained by the reduction of the corresponding nitro compounds that were obtained by the Schiff base condensation of the diketones 11a and 11b and the appropriate o-phenylenediamine

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Section: Resultsmentioning

confidence: 99%

Synthesis of Amino‐ and Bis(bromomethyl)‐Substitued Bi‐ and TetradentateN‐Heteroaromatic Ligands: Building Blocks for Pyrazino‐Functionalized Fullerene Dyads

Kleineweischede¹,

Mattay²

2006

Eur J Org Chem

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“…Mounting medium Fluro-gel II containing DAPI was procured from Electron Microscopy Sciences, (Hatfield, PA, USA). The complexes, [ 1 ]Cl 2 (35) [ 2 ]Cl 4 (36) [(phen) 2 Ru(tpphz)]Cl 2 (36, 37), [ 3 ]Cl 2 (38), [ 4 ]Cl 4 (39), and select enantiomers, Δ- 1 2+ and Λ- 1 2+ ,(35) Δ- 3 2+ and Λ- 3 2+ ,(38) and diastereomers, ΔΔ- 3 4+ , ΛΛ- 3 4+ and ΔΛ- 3 4+ ,(40) were prepared previously described. Enantiopurity was ascertained using chiral HPLC as described in ref (35) and was 97% or greater for all complexes.…”

Section: Methodsmentioning

confidence: 99%

Regression of Lung Cancer by Hypoxia-Sensitizing Ruthenium Polypyridyl Complexes

Yadav

Janaratne

Krishnan

et al. 2013

Molecular Cancer Therapeutics

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The ruthenium (II) polypyridyl complexes (RPCs) Δ-[(phen)2Ru(tatpp)]Cl2 (Δ-[3]Cl2) and ΔΔ-[(phen)2Ru(tatpp)Ru(phen)2]Cl4 (ΔΔ-[4]Cl4) are a new generation of metal-based anti-tumor agents. These RPCs bind DNA via intercalation of the tatpp ligand which itself is redox-active and easily reduced at biologically relevant potentials. We have previously shown that RPC 44+ cleaves DNA when reduced by glutathione to a radical species, and that this DNA cleavage is potentiated under hypoxic conditions in vitro. Here we show that 32+ also exhibits free-radical mediated DNA cleavage in vitro, and that 32+ and 44+ both exhibit selective cytotoxicity towards cultured malignant cell lines, and marked inhibition of tumor growth in vivo. The murine acute toxicity of RPCs 32+ and 44+ (maximum tolerable doses (MTD’s) ~ 65 µmol/kg) is comparable with that for cisplatin (LD50 ~57 µmol/kg) but unlike cisplatin, RPC’s are generally cleared from the body unchanged via renal excretion without appreciable metabolism or nephrotoxic side effects. RPCs 32+ and 44+ are demonstrated to suppress growth of human non-small cell lung carcinoma (~83%), show potentiated cytotoxicity in vitro under hypoxic conditions, and induce apoptosis through both intrinsic and extrinsic pathways. The novel hypoxia-enhanced DNA cleavage activity and biological activity suggest a promising new anti-cancer pharmacophore based on metal complexes with aromatic ligands that are easily reduced at biologically accessible potentials.

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“…Deprotection of the tosyl groups was carried out in concentrated sulfuric acid to give 6 in near quantitative yield. Our synthetic approach leading to 6 differs from the one described by Lehn et al [20] in that no further purifi- (DppztBuSalH 2 ) 2ϩ ] (11) was easily metallated using nickel() acetate according to usual procedures. [36] Compounds 11 and 12 were purified for photophysical measurements, by chromatography on a neutral alumina column using dichloromethane/methanol (95:5 and 90:10, respectively) as eluents, and the desired compounds were collected as the first major fraction in both cases.…”

Section: Synthesismentioning

confidence: 99%

A Rigid Molecular Scaffold Affixing a (Polypyridine)ruthenium(II)‐ and a Nickel(II)‐Containing Complex: Spectroscopic Evidence for a Weakly Coupled Bichromophoric System

et al. 2003

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The synthesis of DppztBuSalH2 (7), a rigid conjugated ditopic ligand containing a Dppz (dipyrido[3,2‐a:2′,3′‐c]phenazine) skeleton and a salophen‐type chelate, is reported. The complexes DppztBuSalNi (10), [Ru(bpy)2(DppztBuSalH2)]2+ (11), and [Ru(bpy)2(DppztBuSalNi)]2+ (12) have been prepared and characterised using common spectroscopic methods. Electrochemical, UV/Vis spectroelectrochemical and EPR studies were conducted on compounds 7, 10, 11, and 12. The singly reduced radical forms of 7 and 10 can be generated electrochemically, with the lone electron located on the low‐lying phenazine π*‐molecular orbital. Complexes 11 and 12 show several reduction waves and electronic and EPR data obtained for the electrogenerated singly reduced species show them to be closely related to the radical species 7·− and 10·−, respectively. The presence of nickel(II) in compound 12 renders the addition of the second electron on the phenazine group reversible. Both 11 and 12 show common features on the cathodic side of their cyclic voltammograms, with reversible one‐electron ruthenium‐centred oxidation. An additional low‐potential reversible‐oxidation wave is observed for 12, and this is ascribed to oxidation of the nickel(II) ion. The combined spectroscopic data best describe the ruthenium‐containing complexes as weakly coupled bichromophoric systems. Photophysical studies attest to the formation of a charge‐separated state for 11, whereas a strong quenching is detected for 12. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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Stereoisomerically controlled inorganic architectures: synthesis of enantio- and diastereo-merically pure ruthenium–palladium molecular rods from enantiopure building blocks

Cited by 85 publications

References 21 publications

Synthesis of Amino‐ and Bis(bromomethyl)‐Substitued Bi‐ and TetradentateN‐Heteroaromatic Ligands: Building Blocks for Pyrazino‐Functionalized Fullerene Dyads

Synthesis of Amino‐ and Bis(bromomethyl)‐Substitued Bi‐ and TetradentateN‐Heteroaromatic Ligands: Building Blocks for Pyrazino‐Functionalized Fullerene Dyads

Regression of Lung Cancer by Hypoxia-Sensitizing Ruthenium Polypyridyl Complexes

A Rigid Molecular Scaffold Affixing a (Polypyridine)ruthenium(II)‐ and a Nickel(II)‐Containing Complex: Spectroscopic Evidence for a Weakly Coupled Bichromophoric System

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