Absolute configuration assignment of 3-oxindolylacetyl-4-phenyloxazolidinone derivatives

Suárez‐Castillo, Oscar R.; Meléndez-Rodrı́guez, Myriam; Castelán-Duarte, Luis E.; Zúñiga-Estrada, Erick A.; Cruz-Borbolla, Julián; Morales‐Ríos, Martha S.; Joseph‐Nathan, Pedro

doi:10.1016/j.tetasy.2011.11.018

Cited by 10 publications

(3 citation statements)

References 50 publications

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“…IR spectroscopy itself can, in some cases, also be used to determine the relative stereochemistry, and the combination of VCD with IR appears promising for assigning the stereochemistry if the spectra are analyzed in detail. The number of applications of VCD for the determination of the AC of diastereoisomers increases every year, − but in most cases the relative stereochemistry is already known. In the present study, the AC of all stereoisomers of tadalafil is established from VCD.…”

Section: Introductionmentioning

confidence: 99%

Stereochemistry of the Tadalafil Diastereoisomers: A Critical Assessment of Vibrational Circular Dichroism, Electronic Circular Dichroism, and Optical Rotatory Dispersion

Qiu¹,

Gussem

Tehrani³

et al. 2013

J. Med. Chem.

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The stereochemistry of all four stereoisomers of tadalafil is determined using vibrational circular dichroism (VCD), electronic circular dichroism (ECD), and optical rotatory dispersion (ORD) spectroscopy. By comparing experimentally obtained VCD spectra to computationally simulated ones, the absolute configuration of the enantiomeric pair (6R, 12aR)/(6S, 12aS) can be confidently assigned without prior knowledge of their relative stereochemistry. IR and NMR spectra are used to aid the assignment of the relative stereochemistry. The IR and VCD difference spectra further confirm the assignment of all stereoisomers. ECD and ORD spectra are used to investigate the complementarity of the three chiroptical techniques. VCD spectroscopy itself is found to have the ability to identify diastereoisomers, and simultaneous use of these chiroptical spectroscopic methods and NMR chemical shifts aids in increasing the reliability of stereochemistry assignment of diastereoisomers.

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Section: Introductionmentioning

confidence: 99%

Stereochemistry of the Tadalafil Diastereoisomers: A Critical Assessment of Vibrational Circular Dichroism, Electronic Circular Dichroism, and Optical Rotatory Dispersion

Qiu¹,

Gussem

Tehrani³

et al. 2013

J. Med. Chem.

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“…Moreover, the 6R-cedrol and 6S-isocedrol distinction using IR spectroscopy solely was not possible, likely due to their stereo resemblances, since these epimers vary in the AC of one chiral center among the other four. VCD has been successfully employed to distinguish diastereomers in a number of cases that, summarized by the number of recognized chiral centers from their multiple chiral centers structures, are as follows: one chiral center within two, [20][21][22] within three, 23 within four, [24][25][26] within five, 19,27 within six, 28 within nine, 29 within ten 30 ; two chiral centers within four, 24,25,31 within five, 32 within seven 33 ; three chiral centers within four, 24,25 and within five, 32 and the theoretical distinction of epimers or inverse epimers. 34 Nevertheless, VCD in isolation could not unequivocally distinguish the AC of diastereomeric esters of hibiscus and garcinia acids.…”

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confidence: 99%

Vibrational Circular Dichroism Discrimination of Diastereomeric Cedranol Acetates

Gordillo-Román¹,

Camacho-Ruiz²,

Bucio³

et al. 2013

Chirality

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The reliability of vibrational circular dichroism (VCD) spectroscopy to discriminate four diastereomeric cedranol acetates 1-4 by means of their absolute configuration is examined. The usage of CompareVOA software to quantify comparisons of the measured infrared (IR) and VCD spectra with the corresponding simulated spectra at the B3LYP/DGDZVP and B3PW91/DGDZVP levels of theory for each diastereomer enabled the B3PW91 functional to be qualified as superior to the B3LYP functional for vibrational calculations of 1-4. Analogously, a set of quantitative VCD spectra cross-comparisons of 1-4 unambiguously distinguished the diastereomers using B3PW91 and failed using B3LYP. Remarkably, quantitative IR spectra cross-comparisons of 1-4 using B3PW91 or B3LYP functionals demonstrated that the achiral spectroscopic IR technique is not able to distinguish cedranol acetate diastereomers. VCD comparisons using anisotropy g-factor values of bands in the 1550-950 cm(-1) region of the spectra were of aid to facilitate visual spectra matching for each diastereomer.

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“…The method became much more popular when algorithms appeared that allowed the interpretation of the spectra through comparison with theoretically obtained ones . The number of applications of VCD for the determination of the AC of diastereoisomers increases every year, and in many cases the relative stereochemistry is already known. The purpose of the present paper is to show the strength of VCD to determine the ACs of all stereoisomers of brivaracetam with no prior knowledge of their relative stereochemistry.…”

Section: Methodsmentioning

confidence: 99%

Stereochemistry of the Brivaracetam Diastereoisomers

et al. 2016

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The stereochemistry of all four stereoisomers of brivaracetam was determined using vibrational circular dichroism (VCD) spectroscopy. By comparing experimentally obtained VCD spectra and computationally simulated ones, the absolute configurations can be confidently assigned without prior knowledge of their relative stereochemistry. Neither the corrected mean absolute errors analysis of the nuclear magnetic resonance (NMR) data, nor the matching of experimental and calculated infrared spectra allowed the diastereoisomers to be distinguished. VCD spectroscopy itself suffices to establish the absolute configurations of all diastereoisomers. The relative stereochemistry could also be statistically confirmed by matching experimental and computed NMR spectra using the CP3 algorithm. The combination of VCD and NMR is recommended for molecules bearing more than one chiral center, as the relative configurations obtained from NMR serve as an independent check for those established with VCD. Analysis of the calculated VCD spectra reveals that the localized NH2 scissoring mode at around 1600 cm‐1 is characteristic for intramolecular hydrogen bonding, while the orientation of the ethyl group is reflected by the delocalized modes between 1150 and 1050 cm‐1. Chirality 28:215–225, 2016. © 2016 Wiley Periodicals, Inc.

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Absolute configuration assignment of 3-oxindolylacetyl-4-phenyloxazolidinone derivatives

Cited by 10 publications

References 50 publications

Stereochemistry of the Tadalafil Diastereoisomers: A Critical Assessment of Vibrational Circular Dichroism, Electronic Circular Dichroism, and Optical Rotatory Dispersion

Stereochemistry of the Tadalafil Diastereoisomers: A Critical Assessment of Vibrational Circular Dichroism, Electronic Circular Dichroism, and Optical Rotatory Dispersion

Vibrational Circular Dichroism Discrimination of Diastereomeric Cedranol Acetates

Stereochemistry of the Brivaracetam Diastereoisomers

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