Catalysis of a 1,3-dipolar reaction by distorted DNA incorporating a heterobimetallic platinum(II) and copper(II) complex
Fecha
2017-08-11Autor
Rivilla, Iván
de Cózar, Abel
Schäfer, Thomas
Hernandez, Frank J.
Bittner, Alexander J.
Eleta-Lopez, Aitziber
Aboudzadeh, Ali
Santos, José I.
Miranda, José I.
Cossío Mora, Fernando Pedro
Metadatos
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Chem. Sci. 2017, 8, 7038
Resumen
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) [pi4s + pi2s] mechanisms leading to the exclusive formation of racemic endo-cycloadducts.