A Cyclic Voltammetry Study of the Cation Radical Catalyzed Oxygenation of Tetraalkyl Olefins to Dioxetanes

Article abstract of DOI:10.1021/ja00282a004

Cyclic voltammetry studies allow estimation of the rate constant for addition of O2 to biadamantylidene cation radical (1^.+) to be 5600 M^-1 s^-1 at room temperature and for the cleavage of biadamantylidene dioxetane cation radical to oxygen and 1^.+ > 800 s^-1.Chlorination of the adamantane skeleton slows the overall rate of oxygen addition, and the face selectivity for oxygenation of 5(Cl) is 25:1 in favor attack from the olefin face syn to the chlorine.The implications of these findings for the mechanism of the reaction are discussed.