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Synlett 2002(8): 1223-1232
DOI: 10.1055/s-2002-32947
ACCOUNT
© Georg Thieme Verlag Stuttgart · New York

Development of the Directed Dihydroxylation Reaction

Timothy J. Donohoe*
Department of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL, UK
Fax: (01865) 275674; e-Mail: timothy.donohoe@chem.ox.ac.uk;
Further Information

Publication History

Received 16 October 2001
Publication Date:
25 July 2002 (online)

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Abstract

The following account describes our work on the development and utilisation of the directed dihydroxylation reaction. Our preliminary thoughts and experiments are described, as is the refinement and rationalisation process that eventually led to discovery of the OsO4/TMEDA reagent. A comprehensive description of the directed dihydroxylation of a variety of alcohols and amides is included, together with a mechanistic interpretation of this oxidation and a guide to the use of our methodology in synthesis.

  • 1 Background to Development of the Directed Dihydroxyl­ation

  • 2 The Directed Dihydroxylation of Allylic Alcohols and Amides

  • 3 Mechanism of the OsO4/TMEDA Promoted Oxidation

  • 4 Control of Stereochemistry in Acyclic Systems

  • 5 Regioselective Directed Dihydroxylations

  • 6 Stereoselective Oxidation of Homoallylic Alcohols and Amides

  • 7 How to Make the Reaction Catalytic in Osmium

  • 8 Natural Product Synthesis Using the Directed Dihydroxyl­ation Reaction

  • 9 Conclusion and Future Directions

Key words

osmium tetroxide - hydrogen bonding - stereocontrol - catalyst - oxidation

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1

Present address: The Dyson Perrins Laboratory, South Parks Road, Oxford, OX1 3QY.

10

Donohoe, T. J. unpublished results.

23

We examined the cleavage of TMEDA based osmate esters with a range of oxidants including amine-N-oxides and K3Fe(CN)6; no reaction was observed.