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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