Stereochemical Determination of Acyclic Structures Based on Carbon−Proton Spin-Coupling Constants. A Method of Configuration Analysis for Natural Products

• Published in: Journal of organic chemistry Vol. 64; no. 3; pp. 866 - 876
• Main Authors: Matsumori, Nobuaki, Kaneno, Daisuke, Murata, Michio, Nakamura, Hideshi, Tachibana, Kazuo
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 05-02-1999
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo981810k

A method for elucidating the relative configuration of acyclic organic compounds was developed on the basis of carbon−proton spin-coupling constants (2,3 J C,H) and interproton spin-coupling constants (3 J H,H). This method is based on the theory that, in acyclic systems, the conformation of adjacent asymmetric centers is represented by staggered rotamers, and their relative stereochemistry can be determined using 2,3 J C,H and 3 J H,H, because the combined use of these J values enables the identification of the predominant staggered rotamer(s) out of the six possible derived from threo and erythro configurations. Detailed conformational analysis for model compounds 1−4 revealed that this method is useful in most cases for assignment of the configuration of acyclic structures occurring in natural products, in which stereogenic methine carbons are often substituted with a methyl or a hydroxy (alkoxy) group. This J-based configuration analysis was applied to the stereochemical elucidation of carboxylic acid 5 derived from zooxanthellatoxin and proven to be a practical method even for natural products with complicated structures.