Determination of Molecular Absolute Configuration: Guidelines for Selecting a Suitable Chiroptical Approach

Superchi, Stefano; Rosini, Carlo; Mazzeo, Giuseppe; Giorgio, Egidio

doi:10.1002/9781118120392.ch12

Cited by 14 publications

(21 citation statements)

References 65 publications

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“…5 However, a reliable comparison between experimental data and computations requires a careful consideration of the environment. In fact, chiroptical properties and spectroscopies are usually measured for systems in the condensed phase (i.e., solutions or pure liquids), and the presence of the solvating environment may affect not only the absolute value but especially the sign of the chiroptical response.…”

Section: Introductionmentioning

confidence: 99%

The Electronic Circular Dichroism of Nicotine in Aqueous Solution: A Test Case for Continuum and Mixed Explicit-Continuum Solvation Approaches

et al. 2015

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In this paper, we extend an integrated QM/MM/polarizable continuum model (PCM) method, which combines a fluctuating charge (FQ) approach to the MM polarization with the PCM, to describe electronic circular dichroism (ECD) spectra of systems in aqueous solution. The main features of the approach are presented, and then applications to the UV and ECD spectra of neutral (S)-nicotine in aqueous solution are reported. The performance of the QM/FQ/PCM is compared with that of the PCM against newly measured UV ECD spectra, which are in agreement with previous findings. The inclusion of specific solvation effects via the QM/FQ/PCM method leads to an improvement in the calculated spectra compared to the experimental findings, though the pure PCM results are still qualitatively correct and are a useful tool for the characterization of the states.

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Section: Introductionmentioning

confidence: 99%

The Electronic Circular Dichroism of Nicotine in Aqueous Solution: A Test Case for Continuum and Mixed Explicit-Continuum Solvation Approaches

et al. 2015

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“…An obvious case are alkanes and nonconjugated alkenes . Although several methods exist based on chromophoric derivatives and/or supramolecular approaches, they are based on chemical derivatization and require at least one reactive functional group such as alcohol, amine, carboxylic acid, etc. Quite often, small nonchromophoric molecules show weak or negligible optical rotation, making the use of this technique also challenging .…”

Section: Methodsmentioning

confidence: 99%

Towards the Limits of Vibrational Circular Dichroism Spectroscopy: VCD Spectra of Some Alkyl Vinylethers

Zinna

2015

Chirality

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Three alkyl vinylethers from our collection of chiral samples were investigated through VCD spectroscopy, in combination with Density Functional Theory (DFT) calculations. Despite the simplicity of the compounds, reproducing all the spectral features is an involved task, since the many significantly populated conformers contribute to the total VCD spectrum with bands which often have opposite signatures. Nevertheless, we show that certain bands can be satisfactorily reproduced by calculation and therefore they may be employed for the determination of absolute configuration in these and similar compounds, for which no simple alternative method is available.

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“…This approach, unlike the computational methods, does not require a precise spectral prediction and often the sign of a single chiroptical data (e.g. the sign of a diagnostic ECD Cotton effect) is sufficient for the absolute configuration assignment . The chiroptical probes described so far are all chromophoric systems and the chiral induction is commonly revealed by the ECD spectra, whereas no examples are reported till now in which OR/ORD data are the output of the chiroptical probe used for the configurational assignment.…”

Section: Introductionmentioning

confidence: 99%

“…the sign of ad iagnostic ECD Cottone ffect) is sufficient for the absolutec onfiguration assignment. [9] The chiroptical probes described so far are all chromophorics ystems and the chiral inductioni sc ommonly revealed by the ECD spectra, [10] whereas no examples are reported till now in whichOR/ORD data are the output of the chiroptical probe used for the configurational assignment. On the contrary,i tw ill be really valuable to obtain ac hiroptical probe system in which the absolute configurationd etectionc ould be achieved by very readily availableO Rm easurements.…”

Section: Introductionmentioning

confidence: 99%

Absolute Configuration Assignment from Optical Rotation Data by Means of Biphenyl Chiroptical Probes

Vergura

Scafato

Belviso

et al. 2019

Chemistry A European J

Self Cite

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A non‐empirical approach for the assignment of the absolute configuration of chiral 2‐alkyl‐substituted carboxylic acids and primary amines by [α]D measurements has been developed. The method requires the conversion of the chiral acids or amines into the corresponding 4,4′‐disubstituted biphenylamides or biphenylazepines, respectively. In these derivatives a central‐to‐axial chirality transfer induces a preferred torsion in the biphenyl moiety revealed by the sign of the biphenyl A band in the ECD spectrum. By 4,4′‐substitution on the biphenyl moiety a redshift of the A band is obtained, leading to an increase of its relative contribution to optical rotation. This allows to reliably establish a direct correlation between the [α]D sign, the biphenyl twist and, then, the substrate absolute configuration. This approach thus constitutes a really practical and reliable method to assign the absolute configuration of chiral carboxylic acids and primary amines by simple and straightforward [α]D measurement, readily obtainable by a routine instrumentation like the polarimeter.

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Determination of Molecular Absolute Configuration: Guidelines for Selecting a Suitable Chiroptical Approach

Cited by 14 publications

References 65 publications

The Electronic Circular Dichroism of Nicotine in Aqueous Solution: A Test Case for Continuum and Mixed Explicit-Continuum Solvation Approaches

The Electronic Circular Dichroism of Nicotine in Aqueous Solution: A Test Case for Continuum and Mixed Explicit-Continuum Solvation Approaches

Towards the Limits of Vibrational Circular Dichroism Spectroscopy: VCD Spectra of Some Alkyl Vinylethers

Absolute Configuration Assignment from Optical Rotation Data by Means of Biphenyl Chiroptical Probes

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