BEDNARSKI, PJ and EHRENSPERGER, E and SCHONENBERGER, H and BURGEMEISTER, T (1991) AQUEOUS CHEMISTRY OF MIXED-AMINE CISPLATIN AND TRANSPLATIN ANALOGS - INTRAMOLECULAR PREFERENCE FOR A KINETIC 6-MEMBERED RING OVER A THERMODYNAMIC 5-MEMBERED RING ORTHO-PLATINATION PRODUCT. INORGANIC CHEMISTRY, 30 (15). pp. 3015-3025. ISSN 0020-1669, 1520-510X
Full text not available from this repository.Abstract
A series or mixed-amine cis- and transplatin analogues, containing benzylamine and 2-phenylethylamine functionalities, were synthesized and the aqueous solution chemistry investigated. The cis- and trans-dichloroplatinum(II) isomers having the neutral ligands ammine and 1,2-bis(4-methoxyphenyl)ethylamine (1 and 4), ammine and 2-(4-methoxyphenyl)-1-phenylethylamine (2 and 5), and ammine and bis(4-methoxyphenyl)methylamine (3 and 6) were synthesized in > 98% isomeric purity. With the aim or investigating the pharmacoactivation of this class of compounds, a reversed-phase HPLC assay was developed for determining the rates of Pt-Cl hydrolysis of the cis-configured isomers. The precolumn addition of KBr to the reaction solutions trapped the aquachloro- and diaquaplatinum hydrolysis products as their bromo adducts. The separations of dichloro-, bromochloro-, and dibromoplatinum complexes allowed the quantification of their time-dependent concentrations, and the hydrolysis rate constants for 1-3 could be determined. It was found that, following Pt-Cl hydrolysis, an intramolecular ortho-platination occurred with 1-6. Proton NMR studies showed that, for the trans-configured 4 and 5, the kinetically favored, six-membered ring cycloplatinated products were formed specifically over the thermodynamic, five-membered ring ones. For the cis-configurated 1, the kinetic product was formed selectively. The six-membered cycloplatinated ring could be converted into the five-membered, thermodynamically favored one by heating in dilute KCl. The implications of these novel findings are discussed from both mechanistic chemical and pharmacological points of view.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | TRANSITION-METAL COMPLEXES; CANCER-CHEMOTHERAPY; PLATINUM COMPLEXES; PALLADIUM(II); DNA; CYCLOMETALLATION; LIGAND; CIS-DIAMMINEDICHLOROPLATINUM(II); CIS-<PT(NH3)2CL2>; CYCLOPALLADATION; |
| Depositing User: | Dr. Gernot Deinzer |
| Last Modified: | 19 Oct 2022 08:46 |
| URI: | https://pred.uni-regensburg.de/id/eprint/54939 |
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