Catalysis of a 1,3-dipolar reaction by distorted DNA incorporating a heterobimetallic platinum(ii) and copper(ii) complex.
نویسندگان
چکیده
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.
منابع مشابه
Catalysis of a 1,3-dipolar reaction by distorted DNA incorporating a heterobimetallic platinum(ii) and copper(ii) complex† †Electronic supplementary information (ESI) available: Experimental details, characterization of cycloadducts and intermediates, computational data. CCDC 1411372 and 1411373. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc02311a
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ورودعنوان ژورنال:
- Chemical science
دوره 8 10 شماره
صفحات -
تاریخ انتشار 2017