A theoretical rationalization of the asymmetric induction in sulfinyl-directed [5C + 2C] intramolecular cycloadditions |
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Authors: | López Fernando Castedo Luis Mascareñas José L |
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Institution: | Departamento de Química Orgánica y Unidad Asociada al CSIC, Universidad de Santiago de Compostela, 15782 Santiago de Compostela, Spain. |
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Abstract: | A computational DFT examination (B3LYP/6-31G and B3LYP/6-311+G//B3LYP/6-31G) of the thermal 5C + 2C] cycloaddditions of 6-acetoxy-3-pyranones and 3-silyloxy-4-pyrones with tethered alkenyl sulfoxides confirms that the high level of diastereofacial selectivity obtained is ultimately due to the preference of the alkenesulfinyl group to adopt a well-defined conformation in the transition state of the reaction. This conformation, which is different from that found in the ground state, is most probably dictated by dipolar interaction effects between the sulfoxide and the oxidopyrylium ylide intermediate. |
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