Browsing by Author "Kuzmin A"

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    Photochemical Triggering of the Bergman and Myers?Saito Cyclizations
    (Australian Journal of Chemistry, 2010) Pandithavidana D R; Kuzmin A; Popik V V
    Two strategies for the photochemical generation of reactive enediyne compounds and their subsequent cycloaromatization to p-benzyne or ?,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 ?-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 ?-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.