Digital Repository

Photochemical Triggering of the Bergman and Myers?Saito Cyclizations

Show simple item record Pandithavidana D R en_US Kuzmin A en_US Popik V V en_US 2014-11-19T04:40:16Z 2014-11-19T04:40:16Z 2010
dc.description.abstract 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. en_US
dc.publisher Australian Journal of Chemistry en_US
dc.title Photochemical Triggering of the Bergman and Myers?Saito Cyclizations
dc.type article en_US
dc.identifier.department Chemistry en_US

Files in this item

Files Size Format View

There are no files associated with this item.

This item appears in the following Collection(s)

Show simple item record

Search Digital Repository


My Account