Universal NMR Databases for Contiguous Polyols

Shuhei Higashibayashi, Werngard Czechtizky, Yoshihisa Kobayashi, Yoshito Kishi

研究成果: Article査読

78 被引用数 (Scopus)

抄録

On the basis of 1,2,3-triols la∼d, 1,2,3,4-tetraols 2a∼h, and 1,2,3,4,5-pentaols 3a∼p, NMR databases with four types of profile-descriptors (13C-, 1H-, and 1H(OH)-chemical shifts and vicinal spincoupling constants) for contiguous polyols are reported. To systematically assess the relative values of these databases, a case study has been conducted on heptaols 4a∼d, through which the γ- and δ- effects have been recognized to refine the 13C and 1H chemical shift profile predicted via an application of the concept of self-contained nature. The magnitudes of γ- and δ- effects depend on a specific stereochemical arrangement of the functional groups present in both the inside and outside of a self-contained box and are significant only for the stereoisomers belonging to a specific sub-group. With the exception of the stereochemical arrangement of functional groups belonging to a specific sub-group, the γ- and δ- effects can, at the first order of approximation, be ignored for the stereochemical analysis of unknown compounds. For the stereoisomers belonging to a specific sub-group, it is necessary to refine, with incorporation of the γ- and δ- effects, the profile predicted at the first order of approximation. With use of heptaols 4a∼d, the values of 3JH, H profiles have been assessed. Two methods, one using profiles consisting of three contiguous 3JH,H constants and the other using profiles consisting of two contiguous 3J H,H constants, have been developed. A stereochemical analysis based on three, or two, contiguous 3JH, H profiles is operationally simplerthan one based on 13C and 1H chemical shift profiles. Therefore, it is recommended to use a 3JH,H profile as the primary device to predict the stereochemistry of unknown polyols and 13C and 1H chemical shift profiles as the secondary devices to confirm the predicted stereochemistry.

本文言語English
ページ(範囲)14379-14393
ページ数15
ジャーナルJournal of the American Chemical Society
125
47
DOI
出版ステータスPublished - 2003 11月 26
外部発表はい

ASJC Scopus subject areas

  • 触媒
  • 化学 (全般)
  • 生化学
  • コロイド化学および表面化学

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