Stability Relationships in Bicyclic Ketones

Abstract

Calculated energy differences between cis- and trans-fused bicyclic ketones are provided for bicyclo[3.3.0]octanones, bicyclo[4.3.0]nonanones, bicyclo[5.3.0]decanones, bicyclo[6.3.0]undecanones and the corresponding hydrocarbons with and without angular methyl groups. The calculations were performed for HF/6-31G* and MP2/6-31G* optimized geometries. The latter were used for subsequent single-point energy MP2/6-311G* calculations. Whenever possible, the calculated energy differences were compared with experimental data and found to correspond well. The ­results of the calculations provide a complete picture of expected energetic differences in bicyclic ketone series and will be useful in both instruction and synthetic planning.

bicyclo[3.3.0]octanones - bicyclo[4.3.0]nonanones - calculated energy differences

References

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Present address: Merck Research Laboratories, Rahway, NJ, USA. E-mail address: [e-mail].

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All quantum mechanical calculations were carried out using Gaussian03 (see ref. 8). Summary of calculations of all molecules in Table [1] , Table [2] , Table [3] , and Table [4] , including all levels of theory, is available on request.