Theoretical studies of a singlet oxygen-releasing dioxapaddlane (1,4-diicosa naphthalene-1,4-endoperoxide)

Theoretical calculations have been used to examine singlet oxygen release from a naphthalene endoperoxide which bears a flexible (CH2)(22) polymethylene lid. Monte Carlo and ONIOM calculations that incorporated semi-empirical and density functional theory predicted the conformational influence of the polymethylene chain in the cycloreversion of dioxapaddlane, 1,4-diicosa naphthalene-1,4-endoperoxide, to O-1(2) and 1,4-diicosa naphthalene. This study attempts to build a connection between O-1(2) generation and jump rope dynamics of the dioxapaddlane. The polymethylene chain appears to function as a gatekeeper for the oxygen. Instead of coming full circle, a semi-circle rotation of the polymethylene bridge protected the peroxide group, limiting the dissociation of O-1(2) from the naphthalene site.