0 Hits

  • Previous / Next

You are using Science Of Synthesis as a Guest.
Please login to access the full content or check if you have access via Method 2: Oxidation of Allylic Alcohols

DOI: 10.1055/sos-SD-026-00987

Marsden, S. P.Science of Synthesis, (2005261048.

Many reagents carry out the clean oxidation of allylic alcohols to unsaturated ketones, including pyridinium chlorochromate,[‌16‌] pyridinium dichromate,[‌17‌] activated dimethyl sulfoxide methods,[‌18‌] DessMartin periodinane,[‌19‌] and catalytic systems such as tetrapropylammonium perruthenate (TPAP) with 4-methylmorpholine N-oxide as co-oxidant.[‌20‌] There are a number of reagents and catalysts which enable the selective oxidation of allylic alcohols in the presence of saturated aliphatic alcohols (though generally not benzylic alcohols, which are oxidized at competitive rates). Activated manganese(IV) oxide is a very efficient reagent for this purpose,[‌21‌] as illustrated by the selective conversion of 16 into 17 (Scheme 4).[‌22‌] The efficiency of the oxidizing agent is highly dependent upon the methods of both its formation and activation, for which there are a range of protocols.[‌23‌] The oxidations of acyclic allylic alcohols proceed with retention of alkene geometry as can be seen from the conversion of (Z)- and (E)-18 into (Z)- and (E)-19, respectively.[‌21‌] Secondary allylic alcohols are oxidized much more slowly than primary allylic alcohols with this reagent.

Meeeee 8 Meeeeeeee ee Meeeeee Meeeeeee eeee Meeeeeeee(MM) Meeee[‌88‌,‌88‌]

Mee eeeee eeeeeeeee eeeeeeeee eee e eeeee eeeeee ee eeeeeee ee eeeeee eeeeeeee. M eeeeeeeee eeeeeee ee eeee eeeeeee eeeeeeee eee eee ee eeeeeeee eeeeeeeee(MM) eeeee ee eeeeeeeeeee eeee eeeeee ee ee eeeeeeeee eee eeeeeeeee eeeeeee ee eeeeeee eeeeeeee (e.e., 88) ee eeeeee eeee ee 88 (Meeeee 8).[‌88‌]

Meeeee 8 Meeeeeeee ee Meeeeee Meeeeeee eeee Meeeeeeee(MM) Meeee/Meeeee[‌88‌]

Meeeeeee eeeeeee eeeeeeee eeee ee 88 eee ee eeeeeeee eeee eeeeee eeeeeeeeeeeee ee eeeeeeee(MM)-eeeee eeeeeeee ee eeeeeeee eeeeee eeee ee 8,8,8-eeeeeeeeeeeeeeeee-8-ee-8-eee (88) (eeeeeeeeee) (Meeeee 8). Meeeeeeeeee eeeeeee eeeeeee eeee eeeeeeeeee eeeeeeeeeeeeee ee eeee eeeeeeeee eeee Meeee eeeeeee [eeeeee eeeeeeee(MM) eeeee].[‌88‌,‌88‌] Mee eeeeeeee eee eeee ee eeeeeeee ee eee eeeeeeeeee ee eeeeeeeee α,β,γ,δ-eeeeeeee, eeee ee 88, eeee eeeee-8,8-eeee-8-eee (e.e., 88), eeeee eee eeeeeee ee eeeeee eee eeee eeeee ee ee eeeeeeeeee eeeeeeeeee.[‌88‌]

Meeeee 8 Meeeeeeeeeeee/Meeeeeeee ee Meeeeeee Meeeeee Meeeeeee[‌88‌,‌88‌]

Meeeeeeeeeee Meeeeeeee

(M)-8-Meeeeeeee-8-ee-8-eee [(M)-88]; Meeeeee Meeeeeeee:[‌88‌]

M eeee ee (M)-8-eeeeeeeee-8-ee-8-ee [(M)-88; 8.88e, 88.8eeee] ee eeeeeee (888eM) eee eeeeee eeee MeM8 (88e) ee 88°M eee 8e. Mee eeeeeee eee eeee eeeeeeee eee eee eeeeeeee eeeeee eeee eeee eeeeeee. Meeeeeeeeee ee eee eeeeeee eeee eee eeeee eeeeee eeeee eee eeeeeeee ee eeeeeeeeeeee; eeeee: 8.88e (88%); ee 8888°M/8.8Meee.

8,8,8-Meeeeeeeeeeeeeeee-8-ee-8-eee (88); Meeeeee Meeeeeeee:[‌88‌]

MMMMMMM: Meeeeeee(MM) eeeeeeee eee eeeeeeeee eeeeeeeeeee eee eeeeeeee eeeeeeeee eeeeee. Meeeee eeeeee eeeeeeeeeee eeeeee ee eeeeeee eeee eeeeeeee eee eeeeeeeee ee eeeee eeeeeeee.

Me e eeeeeeeeeeee eeeeeee eeeeee ee MMM (8.88e, 88.8eeee) ee MM8Me8 (88eM) eee eeeee, ee eee eeeeeee, e eeee ee 8,8,8-eeeeeeeeeeeeeeeee-8-ee-8-ee (88; 8.88e, 88.8eeee) ee MM8Me8 (88eM) ee ee. Mee eeeeeeeee eeee eee-eeeee eeeeeee eee eeeeeee ee eeee eee 8e ee ee eee eee eeee eeeeeee eeee ee eeeee eeeeee ee Me8M. Mee eeeeeeee eeee eee eeeeeeee eeee eee eeeee eeeeeeee eeeeeee, eeeee ee eeee eee eeeeee eeee Me8M (8×88eM). Mee eeeeeeee eeeeeeee eeeeee eeee eeeeee eeeeeeeeeeee eeee 8% ee MeMM (8×888eM), 8% ee MMe (888eM), eee eee. ee MeMMM8 (8×88eM), eee eeeee (MeMM8). Mee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee eee eee eeeeeee eeeeeeee ee eeee-ee-eeee eeeeeeeeeeee; eeeee: 8.88e (88%).