A new chiral oxathiane: synthesis, resolution and absolute configuration determination by vibrational circular dichroism

Solladié‐Cavallo, Arlette; Baláž, Milan; Sališová, Marta; Suteu, Cristina; Nafie, Laurence A.; Cao, Xiaolin; Freedman, Teresa B.

doi:10.1016/s0957-4166(01)00441-4

Cited by 22 publications

(12 citation statements)

References 17 publications

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“…Oxathiane 5H-cis was therefore synthesized and resolved, and its structure and absolute configuration were determined. [9] Here we report the diastereoreactivity at the CH 2 bridge of unprotected and protected oxathiane 5H-cis, 5Bn-cis, and 5Si-cis.…”

Section: Introductionmentioning

confidence: 82%

Diastereoreactivity of a Chiral Oxathiane Derived from 5‐Hydroxy‐1‐tetralone

2002

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The diastereoreactivity at the CH 2 bridge of a cis-oxathiane derived from 5-hydroxy-1-tetralone (unprotected and protected at the OH) was studied, and it appeared that all reactions at C-2 provided equatorial substitution. It was also found that: i) reductions of the equatorial benzoyl derivative with selectrides provided high diastereoselectivities at C-2Ј while LAH did not. Methyl Grignard addition was less selective and the selectivity of the propanoyl analogue was smaller; ii) condensation of aldehydes and/or ketones with the lithio derivative provided high equatorial diastereoselec-

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Section: Introductionmentioning

confidence: 82%

Diastereoreactivity of a Chiral Oxathiane Derived from 5‐Hydroxy‐1‐tetralone

2002

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“…78 Our group has also collaborated with laboratories worldwide on the use of VCD to determine absolute configuration and solution-state conformations. Recent publications include stereochemical analyses of a chiral oxathiane, 79 a chiral 1,4-oxazin-2-one, 80 a vasopressin receptor antagonist, 81 mirtazepine, 82 and (R)-(+)-1-(9-phenanthryl)ethylamine. 83 From our laboratory at Syracuse University, the first VCD calculations on transition metal complexes, (+)-tris(ethylenediaminato)cobalt(III) 41 and Zn sparteine complexes have been published recently.…”

Section: Recent Applications Of Stereochemical Determinationmentioning

confidence: 99%

“…79 Here, the experimental IR and VCD spectra are presented for (+)-5 measured as a solution in CDCl 3 compared to the calculated VCD of the two lowest energy conformers of (S,S)-5 using DFT/6-31G(d)/B3LYP and the VCD subroutines in Gaussian 98. The conformers differ principally only in the orientation of the hydroxyl moiety, and yet significant differences in the VCD spectra result from this small change in conformation.…”

Section: Conformationally Flexible Moleculesmentioning

confidence: 99%

“…One of the simplest examples of simultaneous determination of absolute configuration and conformation population in solution is illustrated in Figure 7 for the case of a new oxathiane molecule, 5, synthesized in the laboratory of Prof. Arlette Solladie-Cavallo. 79 Here, the experimental IR and VCD spectra are presented for (+)-5 measured as a solution in CDCl 3 compared to the calculated VCD of the two lowest energy conformers of (S,S)-5 using DFT/6-31G(d)/B3LYP and the VCD subroutines in Gaussian 98. The conformers differ principally only in the orientation of the hydroxyl moiety, and yet significant differences in the VCD spectra result from this small change in conformation.…”

Section: Conformationally Flexible Moleculesmentioning

confidence: 99%

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Absolute configuration determination of chiral molecules in the solution state using vibrational circular dichroism

Freedman

Cao

Dukor³

et al. 2003

Chirality

504

389

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Advances in the measurement, calculation, and application of vibrational circular dichroism (VCD) for the determination of absolute configuration are described. The purpose of the review is to provide an up-to-date perspective on the capability of VCD to solve problems of absolute stereochemistry for chiral molecules primarily in the solution state. The scope of the article covers the experimental methods needed for the accurate measurement of VCD spectra and the theoretical steps required to systematically deduce absolute configuration. Determination of absolute configuration of a molecule by VCD requires knowledge of its conformation or conformational distribution, and hence VCD analysis necessarily provides solution-state conformation information, in many cases available by no other method, as an additional benefit. Comparisons of the advantages and limitations of VCD relative to other available chiroptical methods of analysis are also presented.

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“…Of special interest is the exquisite sensibility of VCD to conformational flexibility [222]. VCD is so sensitive to molecular conformation that cis and trans conformations show different spectra [225]. It is therefore a sensitive probe of the presence of higher energy conformers which cannot be accessed in jet-cooled experiments.…”

Section: Solvation Of Pseudo-enantiomersmentioning

confidence: 99%

Chirality effects in gas-phase spectroscopy and photophysics of molecular and ionic complexes: contribution of low and room temperature studies

Zehnacker‐Rentien

2014

International Reviews in Physical Chemistry

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This review focuses on chirality effects in spectroscopy and photophysics of chiral molecules or protonated ions, and their weakly bound complexes, isolated in the gas phase. Low-temperature studies in jet-cooled conditions allow disentangling the different interactions at play and shed light on the ancillary interactions responsible for chiral recognition, like OH…π or CH…π, which would be blurred at room temperature. The consequences of these interactions on chiral recognition in condensed phase are described, as well as the influence of higher energy conformers, which can be accessed in room-temperature experiments. The role of kinetic effects and solvation in jet-cooled experiments is discussed. Last, examples of dramatic chirality effects in photo-induced dissociation are given.

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A new chiral oxathiane: synthesis, resolution and absolute configuration determination by vibrational circular dichroism

Cited by 22 publications

References 17 publications

Diastereoreactivity of a Chiral Oxathiane Derived from 5‐Hydroxy‐1‐tetralone

Diastereoreactivity of a Chiral Oxathiane Derived from 5‐Hydroxy‐1‐tetralone

Absolute configuration determination of chiral molecules in the solution state using vibrational circular dichroism

Chirality effects in gas-phase spectroscopy and photophysics of molecular and ionic complexes: contribution of low and room temperature studies

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