Chiroptical properties of cyclic esters and ketals derived from (S)-1,2-propylene glycol and (S,S)- and (R,R)-2,3-butylene glycol

Usieli, Varda; Pilersdorf, A.; Shor, Sharona; Katzhendler, Jehoshua; Sarel, Shalom

doi:10.1021/jo00928a022

Cited by 20 publications

(3 citation statements)

References 11 publications

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“…Until now, to the best of our knowledge, there are only a few reports on the chiroptical properties of sulfites in the literature 17 and the present results try to resolve this lack to some extent. On the basis of our studies it can be stated that CD spectroscopy is a valuable tool in stereochemical studies on cyclic sulfites.…”

Section: Discussionmentioning

confidence: 59%

Six‐membered cyclic sulfites derived from glucofuranose and 1,2,4‐butanetriol

et al. 2001

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Six-membered cyclic sulfites derived from glucofuranose derivatives 5, 6 and from 1-O-tert-butyldimethylsilil-1,2,4-butanetriol 12 were synthesized and separated into pure diastereomers which were in turn subjected to the sequence of reactions leading to the introduction of the terminal vinyl ether fragment. Reactivity and applicability of cyclic sulfites as intermediates in [2+2]cycloaddition of chlorosulfonyl isocyanate (CSI) to vinyl ethers were studied. The cycloaddition to vinyl ethers 19 and 20 proceeded in low yield and low asymmetric induction, in the case of the former, and moderate yield and pronounced asymmetric induction, in the case of the latter. The (1)H-NMR spectra of sulfites 13-16 reveal a preference of the sulfite oxygen atom for the axial position. Thus, well-defined conformation in solution for compounds 13 and 15 and a mixture of the two possible chair forms for sulfites 14 and 16 could be assigned. The stretching frequency of the S-->O bond in stable conformation with an axial sulfite oxygen occurs in the range 1,160-1,210 cm(-1), whereas conformationally mobile sulfites exhibit corresponding absorption above 1,220 cm(-1). The absolute configuration assignments of sulfites 7, 8, 15, 16 and 25-28 were done empirically based on the combined analysis of the NMR, IR, X-ray, and dichroic data. It was demonstrated that the sign of the Cotton effect around 194 nm correlated with the absolute stereochemistry at the sulfur atom in a sulfite chromophore.

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Section: Discussionmentioning

confidence: 59%

Six‐membered cyclic sulfites derived from glucofuranose and 1,2,4‐butanetriol

et al. 2001

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“…Single-crystal X-ray analysis has been employed to determine the absolute configuration (AC) at the sulfur atom in the diastereomers. Since these cyclic sulfites show absorption maximum in the UV spectral range at around 195−220 nm, it could be expected that an important stereochemical information could be gained from their electronic circular dichroism (CD) spectra. Indeed, Sarel and co-workers have shown that the CD spectra of model cyclic sulfites derived from chiral 1,2-diols reflect the configuration at the sulfur atom.…”

Section: Introductionmentioning

confidence: 99%

“…Since these cyclic sulfites show absorption maximum in the UV spectral range at around 195−220 nm, it could be expected that an important stereochemical information could be gained from their electronic circular dichroism (CD) spectra. Indeed, Sarel and co-workers have shown that the CD spectra of model cyclic sulfites derived from chiral 1,2-diols reflect the configuration at the sulfur atom. More recently, our study on application of the CD in determination of the AC of six-membered cyclic sulfites derived from glucofuranose and 1,2,4-butanetriol revealed the usefulness of CD spectroscopy for this purpose .…”

Section: Introductionmentioning

confidence: 99%

New Insight into Chiroptical Properties of 1,2-Diols Cyclic Sulfites.

et al. 2009

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The present work examines the relationship between the structure and chiroptical properties of cyclic sulfites utilizing the electronic circular dichroism (CD) and time-dependent density functional theory (TD-DFT). For some of the model compounds the study was additionally supported by the X-ray diffraction analysis. A comparison of the experimental and simulated CD spectra gave a reasonable interpretation of the Cotton effects observed in the 200-220 nm spectral range. The study revealed a high sensitivity of the CD spectra with regard to the configuration at the sulfur atom as well as the conformation of the ring bearing the sulfite chromophore. The results demonstrated that such a combined treatment enabled the determination of absolute configuration with a high degree of confidence.

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Verzweigte Zucker, X: Selektive Synthese der D ‐Aldgarose aus Aldgamycin E und F

1976

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Eine selektive Synthese zur 1,2-O-Isopropyliden-Verbindung der im Aldgamycin E und F als Baustein auftretenden D-Aldgarose wird beschrieben. Die 3-Ulose 5 reagiert mit 2-Lithio-2-methyl-1,3-dithian unter Ankniipfung einer aquatorialen Seitenkette. Die Reduktion des Ketons 7 mit NaBH, liefert bevorzugt den L-glycero-Alkohol 11, der in das gewiinschte Carbonat 12 iiberfuhrbar ist. Die Stereochemie der Seitenkette wird durch CD-Messungen des Carbonatchromophors gesichert.Branched-chain Sugars, X" Selective Synthesis of D-Aldgarose from Aldgamycine E and F A selective synthesis of the 1,2-O-isopropylidene compound of u-aldgarose present in aldgamycine E and F is described. The 3-dose 5 reacts with 2-lithio-2-methyl-1.3-dithiane with attachment of an equatorial side chain. Reduction of the ketone 7 with NaBH, leads to preferential formation of the L-glycero alcohol 11, which can be converted into the desired carbonate 12. The stereochemistry of the side chain is verified by c.d. measurements of the carbonate chromophore.

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Chiroptical properties of cyclic esters and ketals derived from (S)-1,2-propylene glycol and (S,S)- and (R,R)-2,3-butylene glycol

Cited by 20 publications

References 11 publications

Six‐membered cyclic sulfites derived from glucofuranose and 1,2,4‐butanetriol

Six‐membered cyclic sulfites derived from glucofuranose and 1,2,4‐butanetriol

New Insight into Chiroptical Properties of 1,2-Diols Cyclic Sulfites.

Verzweigte Zucker, X: Selektive Synthese der D ‐Aldgarose aus Aldgamycin E und F

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