An ONIOM Study of the Bergman Reaction: A Computationally Efficient and Accurate Method for Modeling the Enediyne Anticancer Antibiotics

Publication Date

2001

Description

The Bergman cyclization of large polycyclic enediyne systems that mimic the cores of the enediyne anticancer antibiotics was studied using the ONIOM hybrid method. Tests on small enediynes show that ONIOM can accurately match experimental data. The effect of the triggering reaction in the natural products is investigated, and we support the argument that it is strain effects that lower the cyclization barrier. The barrier for the triggered molecule is very low, leading to a reasonable half-life at biological temperatures. No evidence is found that would suggest a concerted cyclization/H-atom abstraction mechanism is necessary for DNA cleavage.

Journal

Chemical Physics Letters

Volume

347

First Page

505

Last Page

511

Department

Chemistry

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