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Contents Vol 63(7)

Photochemical Triggering of the Bergman and Myers–Saito Cyclizations

Andrei Polukhtine A , Grigori Karpov A , Dinesh R. Pandithavidana A , Alexander Kuzmin A and Vladimir V. Popik A B
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A Department of Chemistry, University of Georgia, Athens, GA 30602, USA.

B Correspondening author. Email: vpopik@uga.edu

Australian Journal of Chemistry 63(7) 1099-1107 https://doi.org/10.1071/CH10185
Submitted: 5 May 2010  Accepted: 24 May 2010   Published: 15 July 2010

Abstract

Two strategies for the photochemical generation of reactive enediyne compounds and their subsequent cycloaromatization to p-benzyne or α,3-didehydrotoluene derivatives are discussed in this account. The first method employs a photo-Wolff reaction of stable 11- or 12-membered ring precursor enediynes containing the 2-diazo-1,3-diketone moiety. Irradiation of these compounds results in ring contraction and the formation of two isomeric enediynes possessing an enolized β-ketoester fragment. One of the isomers undergoes the conventional Bergman cyclization, whereas the other isomerizes into the enyne-allene tautomer, which rapidly cyclizes via a Myers–Saito mechanism. The second strategy consists of replacing the triple bond in a cyclic enediyne or enyne-allene structure with a cyclopropenone group, rendering them thermally stable. Photolysis of cyclopropenones results in efficient decarbonylation and the regeneration of a triple bond, restoring the enediyne π-system. The generation of reactive enediynes by non-resonant two-photon excitation using wavelengths within a ‘phototherapeutic window’ was also demonstrated. Photogenerated enediynes show significant nuclease activity, efficiently inducing single-strand dDNA cleavage.


References


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