TETRAHEDRON
LETTERS
Tetrahedron Letters 39 (1998) 7463-7466
Pergamon
Ultrasound Accelerated Permanganate Oxidation:
An Improved Procedure for the Synthesis of 1,2-Cis diols from Olefins
Rajender S. Varma* and Kannan P. Naicker
Department of Chemistry and Texas Regional Institute for Environmental Studies (TRIES),
Sam Houston State University, Huntsville, Texas 77341-2117, U. S. A.
Fax: (409)-294-1585; E-mail: CHM_RSV@SHSU.EDU
Received 2 July 1998; revised 24 July 1998; accepted 29 July 1998
Abstract: A simple and expeditious method for the preparation of 1,2-cis diols is described from olefins using an
inexpensive oxidant potassium permanganate, KMnO4, via sonochemical activation in aqueous media. © 1998Elsevier
Science Ltd. All rights reserved.
A large number of permanganate reagents have been developed for the oxidation of organic
molecules under heterogeneous conditions. 1 Potassium permanganate supported on silica gel 2
or molecular sieves 3 has been used to oxidize alcohols to carbonyl compounds and for the
cleavage 4a or oxidation 4b of carbon-carbon double bonds, permanganate supported on copper
sulfate pentahydrate has been used for the oxidation of alcohols to the corresponding carbonyl
compounds, 5 diols to lactones, 6 and sulfides to sulfones. 7 Zinc permanganate supported on silica
gel is utilized for the conversion of acetylenes to c~-diketones and cyclic olefins to ketols. 8 The
dihydroxylation of olefins is generally accomplished by osmium tetraoxide, OsO4, 9 and alkaline
potassium permanganate, KMnO4, from the less-hindered side of the double bond. 1° The main
drawback of this reaction is that OsO4 is expensive and highly toxic. Consequently, its use has
been limited to small-scale preparations of scarce materials. Similar results are obtainable more
economically by utilizing H202,11 t-butylhydroperoxide in alkaline media 12 0 r
N-methylmorpholine-N-oxide 13 with judicious use of co-oxidant, OsO4 in smaller amounts.
Potassium permanganate, on the other hand, is a strong oxidizing agent that can readily oxidize
glycols 14 especially under acid and neutral conditions thus limiting its scope for the generation of
glycols. Alkaline permanganate, however, can lead to glycol formation but the yields are seldom
above 50%, although some improvement is feasible by employing phase transfer catalysis, 15 or
extensive stirring in dilute solution. 16 We decided to explore the use of ultrasound irradiation in
this oxidation protocol with KMnO4 which has been successfully applied earlier to a number of
heterogeneous reactions 17 including the Baeyer's test for identifying the alkenes and alkynes. 18
Herein, we report a facile oxidative conversion of olefins to 1,2-cis diols in aqueous media
0040-4039•98•5 - see front matter © 1998 Elsevier Science Ltd. All rights reserved.
PH: S0040-4039(98)01671-2