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Absolute Configuration of Natural Cyclohexene Oxides by Time Dependent Density Functional Theory Calculation of the Optical Rotation:  The Absolute Configuration of (−)-Sphaeropsidone and (−)-Episphaeropsidone Revised

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Dipartimento di Chimica e Chimica Industriale, Università di Pisa, via Risorgimento 35, 56100 Pisa, Italy, Dipartimento di Chimica, Università della Basilicata, via N. Sauro, 85, 85100 Potenza, Italy, and Dipartimento di Scienze del Suolo, della Pianta, dell'Ambiente e delle Produzioni Animali, Università di Napoli Federico II, via Università 100, 80055 Portici, Italy
Cite this: J. Org. Chem. 2007, 72, 18, 6680–6691
Publication Date (Web):August 7, 2007
https://doi.org/10.1021/jo070806i
Copyright © 2007 American Chemical Society
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Abstract

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The optical rotatory power of some natural cyclohexene oxides, such as (+)-chaloxone, 1, (+)-epiepoformine, 2, (+)-epoformine, 3, (+)-epoxidone, 5, (−)-sphaeropsidone, 6, (−)-episphaeropsidone, 7, and the synthetic compound (+)-epitheobroxide, 4, has been calculated by means of the TDDFT/B3LYP method using the 6-31G(d) and aug-cc-pVDZ basis sets, both in the gas phase and in solution by means of the polarizable continuum model. For compounds 1 and 2, which possess high (about 300 units) optical rotations, gas-phase calculations with the smaller basis set are able to reproduce the experimental values both in sign and order of magnitude. By contrast, a larger basis set is required to satisfactorily simulate the OR values of 3 and 4, which show smaller (about 100 units or less) rotations. The inclusion of the solvent effects is different for different compounds; for 1 and 2, it leads to a better agreement between experiment and prediction, while for 3 and 4, the presence of hydrogen bonding groups makes the application of continuum solvation models less satisfactory. For the flexible system 5, the absolute configuration could not be determined using gas-phase calculations and the smaller basis set, but both inclusion of solvent and larger basis set effects are compulsory. It is noteworthy that calculations both in the gas phase and in the solvent lead to a positive rotatory power for the laevorotatory natural compounds 6 and 7 if the ACs reported in the literature are employed to do the theoretical prediction. This strongly indicates that the ACs previously assigned to these compounds in the literature are not correct and that the TDDFT prediction of OR values has become by now a practicable tool for AC assignments.

†

 Università di Pisa.

‡

 Università della Basilicata.

§

 Università di Napoli Federico II.

*

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

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Relative free energies (kcal/mol) and OR values (deg [dm g/cm3]-1) of (2R,3R,4S)-epiepoformine in ethanol with respect to rotation of the OH group. Relative energies (kcal/mol) and OR values (deg [dm g/cm3]-1) of (2R,3R,4R)-epoformine in ethanol with respect to rotation of the OH group. Aug-cc-pVDZ [α]D values (deg [dm g/cm3]-1) of (2R,3R,4R)-epoxidon in methanol with respect to rotation of the −CH2OH group. Relative energies (kcal/mol) and OR values (deg [dm g/cm3]-1) of (2R,3R,4S)-sphaeropsidone in methanol with respect to rotation of the OH group. B3LYP/6-31G(d) optimized geometries of all the conformers of all the compounds in the gas phase and in solution. This material is available free of charge via the Internet at http://pubs.acs.org.

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