cis-Tetrachlorido-bis(indazole)osmium(iv) and its osmium(iii) analogues: paving the way towards the cis-isomer of the ruthenium anticancer drugs KP1019 and/or NKP1339

A unique class of azo porphyrin, 5,10,15,20-tetraphenyl-21-phenylazo-(2-aza-21-carbaporphyrin 1, in which an azophenyl group is embedded in N -confused porphyrin, was synthesized and characterized by 1 H NMR, 13 C NMR, UV-vis absorption, MS, and X-ray crystallographic analysis. Synthesis of 1 was achieved through a coupling reaction of 21-amino N -confused tetraphenylporphyrin with nitrosobenzene and subsequent deoxygenation of resulting azoxy derivative with a trioxo rhenium(VII) N -fused porphyrinato catalyst. The azo-conjugate molecule was exclusively obtained as a trans-isomer and no isomerization to the cis-isomer was observed under thermal or photoirradiation. The absorption spectrum of 1 shows a moderate red-shift due to the effective interaction between the porphyrinic π-system and the connecting azophenyl group. Upon protonation, this effect is essentially lost as a result of removing degeneracy of LUMO and LUMO+1.

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Synthesis and characterization of a β-fused tetraporphyrin-phthalocyanine star-shaped array

Journal of Porphyrins and Phthalocyanines ◽

10.1142/s1088424616500978 ◽

2016 ◽

Vol 20 (08n11) ◽

pp. 1256-1263 ◽

Cited By ~ 1

Author(s):

Federica Mandoj ◽

Giuseppe Pomarico ◽

Frank R. Fronczek ◽

Kevin M. Smith ◽

Roberto Paolesse

Keyword(s):

Nucleophilic Substitution ◽

Condensation Reaction ◽

Visible Spectrum ◽

Synthesis And Characterization ◽

Central Unit ◽

Porphyrin Ring ◽

Synthetic Pathway ◽

Porphyrin Phthalocyanine ◽

The Way

A star-shaped array, consisting in four tetraphenylporphyrin fused to a phthalocyanine central unit by pyrazine groups, is constructed via the condensation reaction of a dicyanoquinoxaline annulated to a porphyrin ring. The nature of the annulated group is critical for the success of the reaction; in the case of smaller linkers, such as a dicyanopyrazine unit, a nucleophilic substitution occurred, giving the corresponding alcoxy derivative in alcoholic solvents. The visible spectrum of the array shows the typical absorptions of the macrocyclic sub units. The synthetic pathway here presented opens the way to the preparation of [Formula: see text]-fused porphyrin-phthalocyanine arrays.

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Synthesis and Characterization of Platinum(IV) Anticancer Drugs with Functionalized Aromatic Carboxylate Ligands: Influence of the Ligands on Drug Efficacies and Uptake

Journal of Medicinal Chemistry ◽

10.1021/jm0506468 ◽

2005 ◽

Vol 48 (25) ◽

pp. 8060-8069 ◽

Cited By ~ 86

Author(s):

Wee Han Ang ◽

Sébastien Pilet ◽

Rosario Scopelliti ◽

François Bussy ◽

Lucienne Juillerat-Jeanneret ◽

...

Keyword(s):

Anticancer Drugs ◽

Synthesis And Characterization ◽

Carboxylate Ligands ◽

Aromatic Carboxylate

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Designing, synthesis, and characterization of some novel coumarin derivatives as probable anticancer drugs

Medicinal Chemistry Research ◽

10.1007/s00044-012-0299-0 ◽

2012 ◽

Vol 22 (9) ◽

pp. 4146-4157 ◽

Cited By ~ 10

Author(s):

Darla Mark Manidhar ◽

Rajesh Kumar Kesharwani ◽

N. Bakthavatchala Reddy ◽

C. Suresh Reddy ◽

Krishna Misra

Keyword(s):

Anticancer Drugs ◽

Synthesis And Characterization ◽

Coumarin Derivatives

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The synthesis and kinetics of isomerization and solvent exchange of the trans-Chloro(dimethyl sulfoxide)bis(ethylenediamine)cobalt(III) ion in dimethyl sulfoxide

Australian Journal of Chemistry ◽

10.1071/ch9810215 ◽

1981 ◽

Vol 34 (1) ◽

pp. 215 ◽

Cited By ~ 6

Author(s):

WG Jackson

Keyword(s):

Exchange Rate ◽

Dimethyl Sulfoxide ◽

Synthesis And Characterization ◽

Aqueous Systems ◽

Solvent Exchange ◽

Kinetics Of ◽

Cis Isomer

The synthesis and characterization of trans-[CO(en)2(Me2SO)Cl](ClO4)2 are described. Its rate of isomerization to the cis isomer has been measured in Me2SO in the range 293-313 K: ktc = 1.54 × 10-3s-1 at 298.2 K, ΔH‡ = 105 kJ mol-1, ΔS‡ = 55 J mol-1 K-1. The solvent exchange rate has been measured by 1H n.m.r. spectroscopy in (CD3)2SO at 308.2K: kex = ktt+ktc = 7.0xl0-3 s-1. These and other data show that trans-to-cis isomerization requires solvent exchange, each act of which leads to substantial rearrangement, c. 90% cis (308.2 K). Differences between non-aqueous and aqueous systems in the steric course of substitution are discussed.

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