0 Hits

  • Previous / Next

You are using Science Of Synthesis as a Guest.
Please login or sign up for a free trial to access the full content. 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]

Meeeee 88 Meeeeeeeee ee 8,8-Meeee eeee α-Meeeeee Meeeeee eeee Meeeeeeeeeeeeeeee[888,888-888]

Meeeeeeeeee 88

M8 M8 Meeeeeeeee Meeee (%) Mee
Me M eeeeeeeeeeeeeeeee (8.8 eeeee), eeeeeee, ee, 8888e 888 [‌888‌]
Me Me eeeeeeeeeeeeeeeee (8.8 eeeee), eeeeeee, ee, 88e 88 [‌888‌]
Me MM8Me eeeeeeeeeeeeeeeee (8×8 eeeee), MM8Me8, ee, 88e 88 [‌888‌]
Me 8-M8MM8M8 eeeeeeeeeeeeeeeee (8 eeeee), MM8Me8, ee, 88e 88e [‌888‌]
(MM8)8Me MM8MM eeeeeeeeeeeeeeeee (8 eeeee), eeeeeee, ee, 88e 88 [‌888‌]
(MM8)8Me MM8M8 eeeeeeeeeeeeeeeee (8 eeeee) eeeeeee, ee, 88e >88 [‌888‌]
Me MM8MMe eeeeeeeeeeeeeeeee (8 eeeee), eeeeeee, ee, 88e 88 [‌888‌]
Me MM8MM8MM eeeeeeeeeeeeeeeee (8 eeeee), eeeeeee, ee, 88e 88e [‌888‌]
(MM8)8Me MM8MMe eeeeeeeeeeeeeeeee (8 eeeee), eeeeeee, ee, 88e >88 [‌888‌]
(MM8)8MMMM eeeeeeeeeeeeeeeee (8.8 eeeee), eeeeeee, ee, 88e >88 [‌888‌]

e Mee 88% ee eee eeeeeeeeeee.

e Mee 88% ee eee eeeeeeeeeee.

Meee eeeeeeeee eeeeee eee,eee-8,8-eeeee eee eeeeeeee eeee eeeeeeeeeeeeeeeee ee eee eeeeeee­eeeeeeee eeeeeeee eee eeeeeeeeeeeee α-eeeeeee eeeeeee eee eeeeeeee ee eeee eeeeeee eeeee ee eeeeeeeeeee ee eee eeeeeeeee ee (8M,8M)-eeeeeeeeeee-8,8-eeee ee (8M)-8-eeeeeeeeeeeeeeeeeeee (888) (Meeeee 88).[‌888‌] Meee e eeeeeee ee eee,eee- eee eeee,eee-eeeeeeeeeeeee ee eeeeeeeeeee-8,8,8-eeeee ee eeeeeeee eeee eeeeeeeeeeeeeeeee eeee 8,8-eeeeeeeeeeeeeeeeeeeeee ee eeeeee.[‌888‌]

Meeeee 88 Meeeeeeeeeeeeee Meeeeeeeee ee (8M,8M)-Meeeeeeeeee-8,8-eeee eeee (8M)-8-Meeeeeeeeeeeeeeeeeee eeee Meeeeeeeeeeeeeeee[‌888‌]

Meeeeeeee eeeeeeeeeeee ee eeeeeee eeeeee eee eeee eeeeeeee eeee eee eeeeee eeeeee ee eeee eeeee eee eeeeeeee eeee eeeeeeeeeeeeeeeee. Meeeeeeee eeeeee eeeeeee ee eee 8- eee 8-eeeeeeeee, eeeeeeeeee eeeeee ee eee 8-eeeeeeee, eee eeee eee eeeee ee eee ee eee 88-eeeeeeee.[‌888‌]

Meeeeeeeeeee Meeeeeeee

Meeeeeeee ee 8,8-Meeee ee α-Meeeeee Meeeeee eeee Meeeeeeeeeeeeeeee: Meeeeeeee ee (8M)-8-Meeeeeeeeeeeeeeeeeee (888); Meeeeee Meeeeeeee:[‌888‌]

Me e eeeeeee eeee ee eee eeeeeeeee (8.88.8eeee) ee eeeeeee (8eM) eee eeeee e 8.88M eeee ee eeeeeeeeeeeeeeeee (8.8 eeeee) ee eeeeeee ee ee. Mee eeeeeee eee eeee eeeeeeee eee 88e. Meeeeee eeeeeee ee eeeeeee eeee eeeee eeeee eee eeeeeee eeeeeeeeee eee eeeeeee. Meeeeeeee eeee eeeeeeeee ee MMM eee MM. Mee eeeeee eeeeeeeee eeeeee ee eeeeeeeeeee ee eee eeeeeee ee eeeee. Mee eeeee eeeeeeee eeee eeeeeeee ee eeeeeeeeeeeeee (eeeeeeeee eeeee/MeMMe ee Me8M) eeee eeeeeeeee.