Absolute stereochemistry of soulattrolide and its analogues

Xiongwei Shi, Athula Attygalle, Adam Liwo, Ming Hong Hao, Jerrold Meinwald, H. Ranjith W. Dharmaratne, W. M.Anoja P. Wanigasekera

Research output: Contribution to journalArticle

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Abstract

The absolute stereochemistry of a group of dipyranocoumarins, some of which are potent inhibitors of HIV-1 reverse transcriptase, was examined. Soulattrolide {2H,6H,10H-benzo[1,2-b:3,4-b':5,6-b'']tripyran-2-one, 11,12- dihydro-12-hydroxy-6,6,10,11-tetramethyl-4-phenyl-, [10S-(10α, 11β, 12β)]- ; CAS Registry No. 65025-62-9} and cordatolide B, two of these dipyranocoumarins, were converted to α-methoxy-α- (trifluoromethyl)phenylacetate (MTPA) derivatives and investigated by 1H NMR spectroscopy. A correlation of 1H NMR chemical shift differences with those predicted by Mosher's concept alone was inadequate to assign confidently the absolute stereochemistries, due to the fact that in both of these molecules too few protons are present on one side of the MTPA plane. However, energetically favored conformations obtained by molecular mechanics calculations provided satisfactory rationalizations for the observed anisotropic shifts in 1H NMR data. The combined results of the two techniques allow us to assign the absolute configuration of both soulattrolide and cordatolide B as (10S, 11R, 12S). The absolute configurations of the other structurally related inhibitors, including inophyllums B, D, and P, costatolide, calanolides A, B, and C, and cordatolide A, are also assigned on the basis of chemical conversions and correlations of their chiroptical properties. Subtleties in the application of the Cahn-Ingold-Prelog rules to the designation of R or S configurations at some positions in these compounds make basically trivial errors particularly easy.

Original languageEnglish (US)
Pages (from-to)1233-1238
Number of pages6
JournalJournal of Organic Chemistry
Volume63
Issue number4
DOIs
StatePublished - Feb 20 1998

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Stereochemistry
calanolide A
Pyranocoumarins
Nuclear magnetic resonance
Molecular mechanics
Chemical shift
Nuclear magnetic resonance spectroscopy
Conformations
Protons
Derivatives
Molecules
soulattrolide
cordatolide A
phenylacetic acid

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

Cite this

Shi, X., Attygalle, A., Liwo, A., Hao, M. H., Meinwald, J., Dharmaratne, H. R. W., & Wanigasekera, W. M. A. P. (1998). Absolute stereochemistry of soulattrolide and its analogues. Journal of Organic Chemistry, 63(4), 1233-1238. https://doi.org/10.1021/jo9717752
Shi, Xiongwei ; Attygalle, Athula ; Liwo, Adam ; Hao, Ming Hong ; Meinwald, Jerrold ; Dharmaratne, H. Ranjith W. ; Wanigasekera, W. M.Anoja P. / Absolute stereochemistry of soulattrolide and its analogues. In: Journal of Organic Chemistry. 1998 ; Vol. 63, No. 4. pp. 1233-1238.
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Shi, X, Attygalle, A, Liwo, A, Hao, MH, Meinwald, J, Dharmaratne, HRW & Wanigasekera, WMAP 1998, 'Absolute stereochemistry of soulattrolide and its analogues', Journal of Organic Chemistry, vol. 63, no. 4, pp. 1233-1238. https://doi.org/10.1021/jo9717752

Absolute stereochemistry of soulattrolide and its analogues. / Shi, Xiongwei; Attygalle, Athula; Liwo, Adam; Hao, Ming Hong; Meinwald, Jerrold; Dharmaratne, H. Ranjith W.; Wanigasekera, W. M.Anoja P.

In: Journal of Organic Chemistry, Vol. 63, No. 4, 20.02.1998, p. 1233-1238.

Research output: Contribution to journalArticle

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AU - Attygalle, Athula

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Shi X, Attygalle A, Liwo A, Hao MH, Meinwald J, Dharmaratne HRW et al. Absolute stereochemistry of soulattrolide and its analogues. Journal of Organic Chemistry. 1998 Feb 20;63(4):1233-1238. https://doi.org/10.1021/jo9717752