Investigation on the Regioselectivities of Intramolecular Oxidation of Unactivated C—H Bonds by Dioxiranes Generated in situ.

Abstract

Oxidation Oxidation O 0212Investigation on the Regioselectivities of Intramolecular Oxidation of Unactivated C-H Bonds by Dioxiranes Generated in situ. -It is found that activated ketones in the presence of Oxone undergo highly regioselective intramolecular oxidation at the δ-position to give tetrahydropyran derivatives. This reaction proceeds with retention of configuration and exhibits strong preference for tertiary C-H bonds over secondary ones. Ketones which do not contain δ-CH bonds can undergo hydrolysis or novel intramolecular oxidation at the γ-position. Starting from the steroid (XIII) remote hydroxylation at C-5 is possible. -(WONG, M.-K.; CHUNG, N.-W.; HE, L.; WANG, X.-C.; YAN, Z.; TANG, Y.-C.; YANG*, D.; J.

Dioxiranes Generated in Situ from Pyruvates and Oxone as Environmentally Friendly Oxidizing Agents for Disinfection

“…Oxone are effective for oxidation of alkenes (22,23), alkanes (24,25,26) and phenols (27). Given the significant success of dioxiranes in green oxidations, it is of interest to explore the activity of these oxidizing agents in disinfection.…”

“…Dioxiranes, either isolated or generated in situ from ketones and Oxone, are powerful oxidizing agents capable of green organic oxidations in aqueous media (16)(17)(18)(19)(20)(21). In particular, our previous studies have demonstrated that dioxiranes generated in situ from pyruvates (R-keto esters) and Oxone are effective for oxidation of alkenes (22,23), alkanes (24)(25)(26), and phenols (27). Given the significant success of dioxiranes in green oxidations, it is of interest to explore the activity of these oxidizing agents in disinfection.…”