Stereochemical analysis of β‐keto sulfoxides by circular dichroism |
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| Authors: | Marcin Górecki Maria Annunziata M. Capozzi Gianluigi Albano Cosimo Cardellicchio Lorenzo Di Bari Gennaro Pescitelli |
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| Affiliation: | 1. Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Pisa, Italy;2. Institute of Organic Chemistry, Polish Academy of Sciences, Warsaw, Poland;3. Dipartimento di Chimica, Università di Bari, Bari, Italy;4. CNR ICCOM c/o Dipartimento di Chimica, Bari, Italy |
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| Abstract: | Three β‐keto sulfoxides ( 1–3 ) were synthesized in enantiopure form and investigated by means of circular dichroism (CD) spectroscopy, both in electronic and vibrational range (ECD, VCD), in combination with quantum chemical calculations. For compound 2 , the X‐ray structure was available; thus, the ECD in the solid state was also considered to reveal the differences between the molecular species in both states. Despite the simplicity of all β‐keto sulfoxides under investigation (29 atoms), reproducing even the major spectral VCD features failed for two compounds, making the use of VCD not ideal to assign their absolute configuration in a reliable way. We demonstrated, however, that the use of ECD spectroscopy, both in solution and solid state, can easily, unambiguously, and without any complication simulate all bands by applying the standard protocol for calculations. This study may stimulate the debate on the need of the use of two chiroptical methods simultaneously in the determination of absolute configurations. |
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| Keywords: | chiroptical spectroscopy conformational search density functional calculations solid‐state ECD/TDDFT solvent effects |
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