Chemistry of dioxiranes. 4. Oxygen atom insertion into carbon-hydrogen bonds by dimethyldioxirane

Reactions of dioxiranes with selected oleochemicals

“…Results with the other fatty acids were similar, namely a relatively low conversion occurred corresponding to the consumption of about 20% of the oxidizing agent with the generation of several positional isomers. The nature of the hydrogen abstraction process is probably a concerted insertion of oxygen into a C-H bond rather than one involving the intermediacy of a discrete free radical (17). Nevertheless, some similarity exists between dioxirane oxidations of hydrocarbons (17), our results with fatty acids and radical chlorinations of hydrocarbons (21) in that the reactions have electrophilic character.…”

“…The most exciting prospect is the direct functionalization of hydrocarbons to generate alcohols and ketones. For example, DMDO will react stereospecifically with stereoisomeric 1,2-dimethylcyclohexanes and decalins to produce tertiary al-cohols with retention of configuration (17). We report here an initial evaluation of the C-H insertion reaction using selected fatty acids and the epoxidations of several unsaturated fatty acid esters.…”

Three‐Membered Heterocycles. Structure and Reactivity

“…Epoxides can be prepared by the action of dioxiranes on alkenes under mild conditions and low temperature [334]. For unstable epoxides, such as those derived from enol ethers, dioxirane epoxidation is the method of choice.…”

Kinetics of dimethyldioxirane decomposition in the presence of cumene

“…Arene oxidation by dioxiranes is of great interest. Murray et aL [3,4] have studied the oxidation of toluene, ethylbenzene, cumene and its derivatives by dimethyldioxirane. They have investigated the reaction products and relative reactivities.…”