Some Stability and Stereochemical Considerations of Simple Bicyclo[4.2.0]octanols

Wendy A. Loughlin; Catherine C. Rowen; Michelle A. McCleary

doi:10.1071/CH04288

RESEARCH ARTICLE

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Some Stability and Stereochemical Considerations of Simple Bicyclo[4.2.0]octanols

Wendy A. Loughlin ^A ^B , Catherine C. Rowen ^A and Michelle A. McCleary ^A

+ Author Affiliations

- Author Affiliations

^A School of Science, Eskitis Research Institute, Griffith University, Brisbane QLD 4111, Australia.

^B Corresponding author. Email: w.loughlin@griffith.edu.au

Australian Journal of Chemistry 58(5) 354-361 https://doi.org/10.1071/CH04288
Submitted: 2 December 2004 Accepted: 8 March 2005 Published: 1 May 2005

Abstract

Bicyclooctanols 3 and 4 were formed with control of the stereochemistry at C8 by using an aluminium enolate of cyclohexanone in 1,2-dimethoxyethane. Bicyclooctanols 1 and 3 were stable towards aqueous hydrochloric acid for short times (< 3.5 h), and ring open to a diastereomeric mix of monoalkylated 5 under protic or aprotic conditions in the presence of base (NaOH or lithium diisopropylamide). The rate of ring opening appears to be dependent on reaction temperature. Bicyclooctanols 1, 3, and 4 displayed remarkable stability when heated at reflux in benzene, whereas use of ethanol prompted stereoselective ring opening of 1 and 3 to give individual diastereomers of monoalkylated 5 and ring opening of 4 to give a 50 : 50 mix of diastereomers of 5. This unexpected result was attributed to the stereochemistry of the bicyclooctanol and placement of hydrogen-bonding sites.

Acknowledgments

We gratefully acknowledge financial support from Griffith University and the Australian Research Council (Small Grants Scheme). We thank Professor Peter Healy for discussions regarding the aluminium transition state.

References

Some Stability and Stereochemical Considerations of Simple Bicyclo[4.2.0]octanols

Abstract

Acknowledgments

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