jp9b08375_si_001.pdf (1.15 MB)
Unbiased Determination of Absolute Configurations by vis-à-vis Comparison of Experimental and Simulated Spectra: The Challenging Case of Diplopyrone
journal contribution
posted on 2019-10-18, 13:33 authored by Marco Fusè, Giuseppe Mazzeo, Giovanna Longhi, Sergio Abbate, Marco Masi, Antonio Evidente, Cristina Puzzarini, Vincenzo BaroneA 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-à-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.
History
Usage metrics
Categories
Keywords
absorptionExperimentalpracticeconjunctionvibrationalapproachquantum-mechanical simulationsstability evaluationvibronic couplingsdispersion contributionsconformer searchspectroscopieKey featuresconfigurationUnbiased Determinationdouble-hybrid functionalsinclusionchiral moleculesSimulated Spectradichroism spectrabasis setsexperimental-computational strategydeterminationtwo-level toolprocedureadAbsolute Configurationsreliabilityperturbation theoryanharmonicityDiplopyronero-vibrationaluser-friendly VMS softwareACdiplopyronevis-aphytotoxic metabolite
Licence
Exports
RefWorks
BibTeX
Ref. manager
Endnote
DataCite
NLM
DC