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Catalysis of a 1,3-dipolar reaction by distorted DNA incorporating a heterobimetallic platinum(ii) and copper(ii) complex.

ABSTRACT: A novel catalytic system based on covalently modified DNA is described. This catalyst promotes 1,3-dipolar reactions between azomethine ylides and maleimides. The catalytic system is based on the distortion of the double helix of DNA by means of the formation of Pt(ii) adducts with guanine units. This distortion, similar to that generated in the interaction of DNA with platinum chemotherapeutic drugs, generates active sites that can accommodate N-metallated azomethine ylides. The proposed reaction mechanism, based on QM(DFT)/MM calculations, is compatible with thermally allowed concerted (but asynchronous) [?4s + ?2s] mechanisms leading to the exclusive formation of racemic endo-cycloadducts.

SUBMITTER: Rivilla I

PROVIDER: S-EPMC5637124 | biostudies-literature | 2017 Oct

REPOSITORIES: biostudies-literature

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Catalysis of a 1,3-dipolar reaction by distorted DNA incorporating a heterobimetallic platinum(ii) and copper(ii) complex.

Rivilla Iván I de Cózar Abel A Schäfer Thomas T Hernandez Frank J FJ Bittner Alexander M AM Eleta-Lopez Aitziber A Aboudzadeh Ali A Santos José I JI Miranda José I JI Cossío Fernando P FP

Chemical science 20170822 10

A novel catalytic system based on covalently modified DNA is described. This catalyst promotes 1,3-dipolar reactions between azomethine ylides and maleimides. The catalytic system is based on the distortion of the double helix of DNA by means of the formation of Pt(ii) adducts with guanine units. This distortion, similar to that generated in the interaction of DNA with platinum chemotherapeutic drugs, generates active sites that can accommodate <i>N</i>-metallated azomethine ylides. The proposed ...[more]

PMID: 29147531

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