Catalysis of a 1,3-dipolar reaction by distorted DNA incorporating a heterobimetallic platinum(ii) and copper(ii) complex†
Iván
Rivilla, 
a
Abel
de Cózar,
ab
Thomas
Schäfer,
bc
Frank J.
Hernandez,
c
Alexander M.
Bittner,
cd
Aitziber
Eleta-Lopez,
d
Ali
Aboudzadeh,
c
José I.
Santos,
e
José I.
Miranda
e
and
Fernando P.
Cossío
*a
a
Abel
de Cózar,
ab
Thomas
Schäfer,
bc
Frank J.
Hernandez,
c
Alexander M.
Bittner,
cd
Aitziber
Eleta-Lopez,
d
Ali
Aboudzadeh,
c
José I.
Santos,
e
José I.
Miranda
e
and
Fernando P.
Cossío
*a
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) [π4s + π2s] mechanisms leading to the exclusive formation of racemic endo-cycloadducts.
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