Crystal and molecular structure of the levorotatory (1R,2S)-ephedrinium (S)-t-butylsulfinylacetate: a definitive proof of the absolute configuration of enantiomeric t-butyl methyl sulfoxides

Drabowicz, J.; Dudziński, Bogdan; Mikołajczyk, M.; Wieczorek, Michał W.; Majzner, Wiesław R.

doi:10.1016/s0957-4166(98)00110-4

Cited by 15 publications

(8 citation statements)

References 21 publications

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“…The work of Drabowicz et al [20] confirmed the AC deduced by Axelrod et al [6] and eliminated the possibility that this might be in error. The utility of our study thus lies principally in demonstrating both the reliability [a] n in cm À1 ; D in 10 À40 esu 2 cm 2 ; R in 10 À44 esu 2 cm 2 .…”

Section: Discussionmentioning

confidence: 70%

“…Subsequently, additional methods for the synthesis of enantiomers of 1 have been reported; [8±16] 1 has been used in evaluating the efficacy of a variety of chiral shift reagents for the determination of enantiomeric excess (ee) in chiral sulfoxides; [17±19] and the AC of 1 has been confirmed through X-ray crystallography of the derivative (1R,2S)-ephedrinium-(S)-tert-butylsulfinylacetate. [20] The purpose of this work is to investigate the utility of VCD spectroscopy [4,21,22] in elucidating the AC of chiral sulfoxides. There have been no prior VCD studies of chiral sulfoxides.…”

Section: Introductionmentioning

confidence: 99%

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Vibrational Circular Dichroism and Absolute Configuration of Chiral Sulfoxides:tert-Butyl Methyl Sulfoxide

et al. 2000

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Mid-infrared vibrational unpolarised absorption and vibrational circular dichroism (VCD) spectra of CCl4 solutions of tert-butyl methyl sulfoxide (1) are reported. The spectra are compared to ab initio density functional theory (DFT) calculations carried out using two functionals, B3PW91 and B3LYP, and two basis sets, 6-31G* and TZ2P. The VCD spectra are calculated using Gauge-invariant atomic orbitals (GIAOs). The analysis of the VCD spectrum confirms the R(-)/S(+) absolute configuration of 1. The advantages and disadvantages of VCD spectroscopy in determining the absolute configurations of chiral sulfoxides are discussed.

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Section: Discussionmentioning

confidence: 70%

Section: Introductionmentioning

confidence: 99%

Vibrational Circular Dichroism and Absolute Configuration of Chiral Sulfoxides:tert-Butyl Methyl Sulfoxide

et al. 2000

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“…Stereochemical Correlations. The addition of MeMgBr to 2 affords the known ( S )- tert -butyl methyl sulfoxide ( 9a ) indicating that 2 is the R isomer. The addition of lithium piperidide to ( R )- 2 is expected to deliver 7d with an R configuration at sulfur (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

Catalytic Asymmetric Oxidation oftert-Butyl Disulfide. Synthesis oftert-Butanesulfinamides,tert-Butyl Sulfoxides, andtert-Butanesulfinimines

et al. 1998

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The first example of the catalytic asymmetric oxidation of tert-butyl disulfide (1) is described. The product, tert-butyl tert-butanethiosulfinate (2) is obtained with 91% enantiomeric excess in yields of ≥92% on scales as large as 1 mol. The application of H2O2 as stoichiometric oxidant in the presence of 0.25 mol % of VO(acac)2 and 0.26 mol % of a chiral Schiff base ligand, 6a, is both convenient and cost-effective. Thiosulfinate ester 2 is chemically and optically stable and serves as an excellent precursor to chiral tert-butanesulfinyl compounds by the stereospecific nucleophilic displacement of tert-butyl thiolate. Addition of LiNH2 in liquid ammonia and THF provides tert-butanesulfinamide (3; 91% yield). A single recrystallization provides enantiomerically pure 3 in 71−75% overall yield from disulfide 1. Enantiomerically pure thiosulfinate ester 2 also reacts readily and stereospecifically with Grignard reagents, organolithiums, lithium amides, and lithium imine salts to provide enantiomerically pure chiral sulfoxides, sulfinamides, and sulfinimines in good yield.

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“…Scheme 2 Representative configurational assignments. from reactions of non-racemic 1 ϩ BF 4 Ϫ and sulfoxide d, and (3) the literature configuration of non-racemic d (which has sometimes been a point of confusion) 21. …”

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confidence: 99%

Synthesis, structure, and interconversion of chiral rhenium oxygen- and sulfur-bound sulfoxide complexes of formula [(η5-C5H5)Re(NO)(PPh3)(OS(Me)R)]+ X−; diastereoselective oxidations of coordinated methyl alkyl sulfides †

Otto

Boone

Arif

et al. 2001

J. Chem. Soc., Dalton Trans.

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Reactions of the chiral chlorobenzene complex [(η 5 -C 5 H 5 )Re(NO)(PPh 3 )(ClC 6 H 5 )] ϩ BF 4Ϫ (1 ϩ BF 4 Ϫ ) and alkyl methyl sulfoxides O᎐ ᎐ S(Me)R (R = a, Me; b, Et; c, i-Pr or d, t-Bu), at Ϫ15 ЊC gave the oxygen-bound sulfoxide complexesϪ ; 96-20%). The triflate salts 2c,2d ϩ TfO Ϫ and 3b,3c ϩ TfO Ϫ are analogously prepared from (η 5 -C 5 H 5 )Re(NO)(PPh 3 )(OTf). Complexes 2b-2d ϩ X Ϫ and 3b-3d ϩ X Ϫ can exist as two Re, S configurational diastereomers. Stereochemistry is assigned from reactions of (S)-or (R)-1 ϩ BF 4Ϫ with enantiomerically enriched sulfoxides (R)-b-d, and a crystal structure of (S Re R S ,R Re S S )-2d ϩ TfO Ϫ ؒ0.5CH 2 Cl 2 . Relative diastereomer stabilities, and the basis for the divergent kinetic and thermodynamic oxygen/sulfur binding selectivities, are analysed. The alkyl methyl sulfide complexes [(η 5 -C 5 H 5 )Re(NO)(PPh 3 )(S(Me)R)] ϩ X Ϫ and dimethyldioxirane react (acetone, Ϫ20 ЊC) to give 3a-3d ϩ X Ϫ . Diastereoselectivities (3b-3d ϩ X Ϫ ) are fair to good. However, some overoxidation to Ph 3 P᎐ ᎐ O occurs, lowering yields.

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Crystal and molecular structure of the levorotatory (1R,2S)-ephedrinium (S)-t-butylsulfinylacetate: a definitive proof of the absolute configuration of enantiomeric t-butyl methyl sulfoxides

Cited by 15 publications

References 21 publications

Vibrational Circular Dichroism and Absolute Configuration of Chiral Sulfoxides:tert-Butyl Methyl Sulfoxide

Vibrational Circular Dichroism and Absolute Configuration of Chiral Sulfoxides:tert-Butyl Methyl Sulfoxide

Catalytic Asymmetric Oxidation oftert-Butyl Disulfide. Synthesis oftert-Butanesulfinamides,tert-Butyl Sulfoxides, andtert-Butanesulfinimines

Synthesis, structure, and interconversion of chiral rhenium oxygen- and sulfur-bound sulfoxide complexes of formula [(η5-C5H5)Re(NO)(PPh3)(OS(Me)R)]+ X−; diastereoselective oxidations of coordinated methyl alkyl sulfides †

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