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Synthesis 2003(2): 0295-0301
DOI: 10.1055/s-2003-36826
PAPER
© Georg Thieme Verlag Stuttgart · New York

A New Practical Method for the Osmium-Catalyzed Dihydroxylation of Olefins­ using Bleach as the Terminal Oxidant

Gerald M. Mehltrettera, Santosh Bhora, Markus Klawonna, Christian Döblera, Uta Sundermeiera, Markus Eckertb, Hans-Christian Militzerb, Matthias Beller*a
a Institut für Organische Katalyseforschung (IfOK) an der Universität Rostock e.V., Buchbinderstr. 5-6, 18055 Rostock, Germany
Fax: +49(381)4669324; e-Mail: matthias.beller@ifok.uni-rostock.de;
b Bayer AG, 51368 Leverkusen, Germany
Further Information

Publication History

Received 23 September 2002
Publication Date:
22 January 2003 (online)

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Abstract

A general procedure for the osmium-catalyzed dihydroxylation of various olefins using bleach as oxidant is reported for the first time. Aromatic and aliphatic olefins yield the corresponding cis-1,2-diols in the presence of dihydroquinine or dihydroquinidine derivatives (Sharpless ligands) with good to excellent chemo- and enantioselectivities under optimized pH conditions. In the presence of a small excess of bleach as reoxidant fast dihydroxylation takes place even at 0 °C. Under optimum reaction conditions it is possible to dihydroxylate terminal aliphatic and aromatic olefins as well as internal olefins. The low price of the oxidant and the simple handling of bleach make this dihydroxylation variant attractive for further applications.

Key words

asymmetric catalysis - dihydroxylation - homogenous catalysis - osmium - oxidations

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TOF = mol product × mol catalyst-1 × h-1.