Chair-boat equilibria in bicyclo[3.3.1]nonane and some 3- and 3,7-substituted derivatives: Thermodynamic parameters and geometry of the conformers as obtained by molecular mechanics |
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Authors: | JA Peters J MA Baas B Van De Graaf JM Van Der Toorn H Van Bekkum |
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Institution: | Laboratory of Organic Chemistry, Delft University of Technology, Julianalaan 136, Delft, The Netherlands |
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Abstract: | ΔG-Values for conformational equilibria in 3,7-substituted bicyclo3.3.1]nonanes have been obtained by means of epimerisation experiments (cc α bc) and by variable temperature 13C NMR (bc α bb). The results of these experiments fit well with those of molecular mechanics using the Schleyer force field. In bicyclo3.3.1]nonane and 3β-substituted derivatives the cc conformation predominates; however, the bulky 3β-substituent t-butyl, is found to have a destabilizing effect. A 3α-substituent forces the substituted wing into the boat conformation. For the 3α,7α-substituted derivatives the conformational preferences depend on the size of the substituents: for 3α-methyl-7α-t-butylbicyclo3.3.1]nonane the cb and t-bb conformers are of approximately equal enthalpy. The geometries, obtained by the calculations, show that the conformers of bicyclo3.3.1]nonane (cc, bc and t-bb) are all distinctly flattened. The boat wings of bc conformers are not twisted to any extent. The t-bb is the most stable bb conformation. The influence of substitution at positions 3 or 7 is discussed in detail; in general, a bulky substituent such as t-butyl, affects the geometry of both wings of the ring system. The calculated geometries are in good agreement with the conclusions of previous 1H NMR investigations. |
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