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Determination of the Absolute Configuration of Six-Membered-Ring Ketones by 13C NMR

Publication ,  Journal Article
Lemiere, GL; Dommisse, RA; Lepoivre, JA; Alderweireldt, FC; Hiemstra, H; Wynberg, H; Jones, JB; Toone, EJ
Published in: Journal of the American Chemical Society
March 1, 1987

The diastereotopic splitting of the 13C NMR signals of the (2R,3R)-2,3-butanediol acetals of 39 chiral six-membered-ring ketones, including 2- and 3-substituted cyclohexanones, 2-alkyltetrahydropyran-4-ones, and 2- and 3-alkyltetrahydrothiopyran- 4-ones, has been studied. The stereodifferentiation of the six-membered-ring carbon atoms was shown to follow a very regular pattern, which is independent of substituents or of heteroatoms in the ring. Hence, an empirical rule could be deduced which allows the assignment of the absolute configuration of the original ketones from the 13C NMR spectrum of their acetals. The rule is only valid for six-membered-ring ketones having the chair form as the preferred conformation in the acetal. As shown for 11 examples, this rule is not valid for acyclic ketones, cyclopentanones, cycloheptanones, or cyclohexanones and cyclohexenones not having the chair form as the preferred conformation. The rule also permits the interpretation of the 13C NMR spectrum of the (2R,3R)-2,3-butanediol acetals of achiral cyclohexanones (seven examples). The stereodifferentiation is almost exclusively determined by the centers of chirality in the dioxolane ring. © 1987, American Chemical Society. All rights reserved.

Duke Scholars

Published In

Journal of the American Chemical Society

DOI

EISSN

1520-5126

ISSN

0002-7863

Publication Date

March 1, 1987

Volume

109

Issue

5

Start / End Page

1363 / 1370

Related Subject Headings

  • General Chemistry
  • 40 Engineering
  • 34 Chemical sciences
  • 03 Chemical Sciences
 

Citation

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Lemiere, G. L., Dommisse, R. A., Lepoivre, J. A., Alderweireldt, F. C., Hiemstra, H., Wynberg, H., … Toone, E. J. (1987). Determination of the Absolute Configuration of Six-Membered-Ring Ketones by 13C NMR. Journal of the American Chemical Society, 109(5), 1363–1370. https://doi.org/10.1021/ja00239a013
Lemiere, G. L., R. A. Dommisse, J. A. Lepoivre, F. C. Alderweireldt, H. Hiemstra, H. Wynberg, J. B. Jones, and E. J. Toone. “Determination of the Absolute Configuration of Six-Membered-Ring Ketones by 13C NMR.” Journal of the American Chemical Society 109, no. 5 (March 1, 1987): 1363–70. https://doi.org/10.1021/ja00239a013.
Lemiere GL, Dommisse RA, Lepoivre JA, Alderweireldt FC, Hiemstra H, Wynberg H, et al. Determination of the Absolute Configuration of Six-Membered-Ring Ketones by 13C NMR. Journal of the American Chemical Society. 1987 Mar 1;109(5):1363–70.
Lemiere, G. L., et al. “Determination of the Absolute Configuration of Six-Membered-Ring Ketones by 13C NMR.” Journal of the American Chemical Society, vol. 109, no. 5, Mar. 1987, pp. 1363–70. Scopus, doi:10.1021/ja00239a013.
Lemiere GL, Dommisse RA, Lepoivre JA, Alderweireldt FC, Hiemstra H, Wynberg H, Jones JB, Toone EJ. Determination of the Absolute Configuration of Six-Membered-Ring Ketones by 13C NMR. Journal of the American Chemical Society. 1987 Mar 1;109(5):1363–1370.
Journal cover image

Published In

Journal of the American Chemical Society

DOI

EISSN

1520-5126

ISSN

0002-7863

Publication Date

March 1, 1987

Volume

109

Issue

5

Start / End Page

1363 / 1370

Related Subject Headings

  • General Chemistry
  • 40 Engineering
  • 34 Chemical sciences
  • 03 Chemical Sciences