Unbiased Determination of Absolute Configurations by vis-a-vis Comparison of Experimental and Simulated Spectra: The Challenging Case of Diplopyrone

Year: 2019

Authors: Fuse M., Mazzeo G., Longhi G., Abbate S., Masi M., Evidente A., Puzzarini C., Barone V.

Autors Affiliation: Scuola Normale Super Pisa, Piazza Cavalieri 7, I-56126 Pisa, Italy; Univ Napoli Federico II, Complesso Univ Monte S Angelo, Dipartimento Sci Chim, Via Cintia 4, I-80126 Naples, Italy; Univ Bologna, Dipartimento Chim Giacomo Ciamician, Via Selmi 2, I-40126 Bologna, Italy; Univ Brescia, Dipartimento Med Mol & Traslazionale, Viale Europa 11, I-25123 Brescia, Italy; CNR, INO CSMT, Via Branze 45, I-25123 Brescia, Italy

Abstract: A new experimental-computational strategy for the determination of the absolute configuration (AC) of complex chiral molecules is proposed by combining diverse experimental spectroscopies with quantum-mechanical simulations well beyond the current computational practice. Key features are the conformer search and relative stability evaluation performed by a new stochastic two-level tool followed by a vis-a-vis comparison of experimental and computed spectra without any ad hoc adjustment. The entire computational procedure is embedded in the user-friendly VMS software, and its reliability is granted by the inclusion of mechanic/electric/magnetic anharmonicity as well as ro-vibrational and vibronic couplings by means of generalized perturbation theory in conjunction with double-hybrid functionals combined with empirical dispersion contributions and suitable basis sets. To test and validate the new approach, the puzzling case of diplopyrone, a fungal phytotoxic metabolite, has been chosen: the close match between new experimental and simulated infrared absorption and vibrational circular dichroism spectra has led to the unbiased evaluation of its AC.

Journal/Review: JOURNAL OF PHYSICAL CHEMISTRY B

Volume: 123 (43)      Pages from: 9230  to: 9237

KeyWords: VIBRATIONAL CIRCULAR-DICHROISM; FLEXIBLE MOLECULES; DIPLODIA-MUTILA; RAMAN-SPECTRA; BASIS-SETS; PATHOGEN; SPECTROMETER; ASSIGNMENT; CONFORMERS; ACCURACY
DOI: 10.1021/acs.jpcb.9b08375

Citations: 20
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