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26.1.1.2.9 Method 9: Oxidation with Dioxiranes

DOI: 10.1055/sos-SD-026-00003

von Angerer, S.Science of Synthesis, (20052688.

Dimethyl- and methyl(trifluoromethyl)dioxiranes are reactive peroxides which are capable of oxidizing secondary alcohols to ketones.[‌311‌‌313‌] Tertiary hydroxy groups are not attacked by these reagents.[‌312‌] Generally these agents are used for regioselective oxidations of diols and triols. Unlike many other oxidants, dioxiranes do not cleave the CC bond in vicinal diols. When the diol consists of two secondary hydroxy groups, hydroxy ketones 112 are the dominant products (Scheme 74).[‌314‌] Obviously, the carbonyl group formed first deactivates the second hydroxy function. The preferred site of oxidation strongly depends on the substituents at the hydroxylated carbon atoms.[‌315‌] Electron-withdrawing or bulky groups reduce the rate of oxidation. Secondary hydroxy groups are oxidized faster than primary ones.[‌292‌,‌316‌]

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