Gauging the significance of atomic oxygen [O(3p)] in sulfoxide photochemistry.: A method for hydrocarbon oxidation

A liquid-phase photolysis of 1,2-benzodiphenylene sulfoxide, 1, and dibenzothiophene sulfoxide, 2, was used to generate atomic oxygen [O(P-3)] or an equivalent active oxygen species. The reaction for sulfoxide photodeoxygenation was similar to a microwave discharge method for generating O(P-3) atoms in the condensed phase (Zadok, E.; Rubinraut, S.; Mazur, Y. J. Org. Chem. 1987, 52, 38590). Sulfoxide photodeoxygenation is a potentially clean method for O(P-3) production compared to the microwave discharge method. With Argon purging of the sulfoxide sample before photolysis, the method can preclude a secondary oxidation process involving molecular oxygen. Our study focused on the results of oxidation products in the reaction of styrene, 3, and on the dependence of substrates that provided an opportunity to vary the electronic and steric effects. The sulfoxide photochemistry is rationalized with the primary formation of O(P-3) in which a charge-transfer interaction between O(P-3) and substrate precedes oxidation. Functionalization of hydrocarbons takes place under mild photolysis conditions of 1 and 2, which leads to an interesting possibility for the synthetic use of atomic oxygen, O(P-3). Alkanes give principally alcohols. Alkenes give principally epoxides and ketones. For comparison, hydroxyl radicals are more reactive and less selective toward hydrocarbons compared to O(P-3) atoms. On the other hand, O(P-3) atoms balance reactivity and selectivity and involve the oxidation of inert alkanes typically inaccessible to peracid, dioxirane, ozone, and singlet molecular oxygen chemistry. The findings from this study may be useful to those interested in generating high-value oxygenated compounds from readily available petroleum components.