Determination of the absolute configurations of isotopically chiral molecules using vibrational circular dichroism (VCD) spectroscopy: the isotopically chiral sulfoxide, perdeuteriophenyl-phenyl-sulfoxide

Drabowicz, J.; Zając, A.; Łyżwa, P.; Stephens, Philip J.; Pan, Jian‐Jung; Devlin, F. J.

doi:10.1016/j.tetasy.2007.12.014

Cited by 15 publications

(16 citation statements)

References 38 publications

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“…Over the past several years there has been a rapid growth in the use of VCD to determine the AC of small chiral organic molecules. A large variety of structural types have been examined, including epoxides and cyclopropanes, [55][56][57][58] bicyclic and tricyclic structures, [59][60][61][62][63][64][65][66][67] chiral structures with no chiral center (atropisomer or molecules with axial or helical chirality), [68][69][70][71][72][73][74][75][76][77][78][79][80][81][82][83] sulfur or phosphorus containing compounds, 77,[84][85][86][87][88] flexible molecules, 56,[89][90][91] and other structures that do not fit into any of the above categories. [92][93][94][95][96][97] The following examples highlight the versatility of VCD as a powerful tool for the AC determinations of different types of chiral organ...…”

Section: Determination Of Absolute Configuration Of Small Organic Molmentioning

confidence: 99%

“…Enantiopure sulfoxides are valuable chiral starting material and important chiral auxiliaries in organic synthesis. 88 In the past, the AC of optically pure sulfoxides has been determined by the empirical rule of Mislow et al 109 However, a recent non-empirical analy- sis of a series of ECD spectra of chiral alkyl aryl sulfoxides has found the rule to be wrong for these molecules. 110 In this study, the groups of Stephens and Drabowicz synthesized and determined the AC of an isotopically chiral sulfoxide 4 (Fig.…”

Section: Determination Of Absolute Configuration Of Small Organic Molmentioning

confidence: 99%

“…The assignment of the experimental spectrum is based on the B3LYP/TZ2P spectrum of (S)-1. The calculated IR and VCD spectra have Lorentzian band shapes (c = 4.0 cm -1 ) 88. Adapted from Ref 88.…”

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confidence: 99%

“…The calculated IR and VCD spectra have Lorentzian band shapes (c = 4.0 cm -1 ) 88. Adapted from Ref 88. with permission of Elsevier.…”

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confidence: 99%

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Determination of Absolute Configuration of Chiral Molecules Using Vibrational Optical Activity: A Review

Wang²,

Dukor³

et al. 2011

Appl Spectrosc

289

218

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Determination of the absolute handedness, known as absolute configuration (AC), of chiral molecules is an important step in any field related to chirality, especially in the pharmaceutical industry. Vibrational optical activity (VOA) has become a powerful tool for the determination of the AC of chiral molecules in the solution state after nearly forty years of evolution. VOA offers a novel alternative, or supplement, to X-ray crystallography, permitting AC determinations on neat liquid, oil, and solution samples without the need to grow single crystals of the pure chiral sample molecules as required for X-ray analysis. By comparing the sign and intensity of the measured VOA spectrum with the corresponding ab initio density functional theory (DFT) calculated VOA spectrum of a chosen configuration, one can unambiguously assign the AC of a chiral molecule. Comparing measured VOA spectra with calculated VOA spectra of all the conformers can also provide solution-state conformational populations. VOA consists of infrared vibrational circular dichroism (VCD) and vibrational Raman optical activity (ROA). Currently, VCD is used routinely by researchers in a variety of backgrounds, including molecular chirality, asymmetric synthesis, chiral catalysis, drug screening, pharmacology, and natural products. Although the application of ROA in AC determination lags behind that of VCD, with the recent implementation of ROA subroutines in commercial quantum chemistry software, ROA will in the future complement VCD for AC determination. In this review, the basic principles of the application of VCD to the determination of absolute configuration in chiral molecules are described. The steps required for VCD spectral measurement and calculation are outlined, followed by brief descriptions of recently published papers reporting the determination of AC in small organic, pharmaceutical, and natural product molecules.

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Section: Determination Of Absolute Configuration Of Small Organic Molmentioning

confidence: 99%

Section: Determination Of Absolute Configuration Of Small Organic Molmentioning

confidence: 99%

See 2 more Smart Citations

Determination of Absolute Configuration of Chiral Molecules Using Vibrational Optical Activity: A Review

Wang²,

Dukor³

et al. 2011

Appl Spectrosc

289

218

View full text Add to dashboard Cite

show abstract

“…Esters of sulfinic acids have long been used in asymmetric synthesis 11,12 and previous investigations have revealed that these groups can be cleaved by nucleophiles to produce an alcohol and a thiosulfinate. 13,14 The thiophilicity of sulfur-based functional groups is well established 15 and we therefore anticipated that such sulfinate esters might be reactive with biological thiols as well (Scheme 1).…”

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confidence: 99%