Chiral Preparation of C ₂-Symmetric 4-Cyclopentene-1,3-diol

Abstract

Optically pure C₂ -symmetric 4-cyclopentene-1,3-diol has been prepared in both enantiomeric forms from racemic (3aS*,4R*,7S*,7aS*)-3a,4,7,7a-tetrahydro-4,7-methano-1H-inden-1-one by employing lipase-mediated kinetic resolution as the key step. As a result, the known (3aS*,4R*,7S*,7aS*)-3a,4,7,7a-tetrahydro-4,7-methano-1H-inden-1-one is transformed into (1′S*,3′S*,3′aR*,4′S*,7′R*,7′aS*)- 2′,3′,3′a,4′,7′,7′a-hexahydro-3′-hydroxy-4′,7′-methano-1′H-inden-1′-yl benzoate, via stereo- and regioselective hydride reduction of epoxy ketone and sequential benzoylation, which is resolved under transesterification conditions in the presence of lipase. The hydride reduction of benzoate and acetate gives the corresponding chiral diols, which are further transformed into both enantiomers of C₂ -symmetric 4-cyclopentene-1,3-diol via a retro-Diels-Alder reaction.

Key words

enzymes - stereoselective synthesis - Diels-Alder reactions - diols - epoxides

References

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11

Preliminary results of this work were presented at The 5 ^th International Symposium on Biocatalysis and Biotransformation, Darmstadt: Germany, September 2-7, 2001, see abstracts p. 353.

15

All of the lipases we used were commercially available from Amano Enzyme Inc., Japan. The origin of each lipase is summarized in the Table.