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Applying B3LYP/6-31+G(d) methodology, which was previously shown to be adequate, see: (a) Reference 12.
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Applying B3LYP/6-31+G(d) methodology, which was previously shown to be adequate, see: (a) Reference 12.
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77949861492
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Conformational search was done at the AM1 level of theory, using SPARTAN; Wavefunction, Inc. All obtained conformers within a 5 kcal/ mol energy range were subsequently optimized with B3LYP/6-31+G(d) in Gaussian03.
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Conformational search was done at the AM1 level of theory, using SPARTAN; Wavefunction, Inc. All obtained conformers within a 5 kcal/ mol energy range were subsequently optimized with B3LYP/6-31+G(d) in Gaussian03.
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Figures created with: CYLview, 1.0b; Legault, C. Y., Université de Sherbrooke, 2009 (http://www.cylview.org).
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Figures created with: CYLview, 1.0b; Legault, C. Y., Université de Sherbrooke, 2009 (http://www.cylview.org).
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77949860711
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We calculated the silyl analogue of E'-6-boat-TS with OTMS instead of OMe. The activation barrier of the rearrangement is 25.8 kcal/mol and the free energy of reaction is -32.9 kcal/mol, indicating that the OMe model is adequate.
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We calculated the silyl analogue of E'-6-boat-TS with OTMS instead of OMe. The activation barrier of the rearrangement is 25.8 kcal/mol and the free energy of reaction is -32.9 kcal/mol, indicating that the OMe model is adequate.
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