The complete assignment of the proton and carbon chemical shifts of 6‐O‐acetyl‐2,3,4‐tri‐O‐(3S‐methylpentanoyl)‐α‐D‐glucopyranosyl‐β‐D‐fructofuranoside, a naturally occurring flavor precursor of tobacco, is presented. These assignments were made by comparison of the spectra obtained from 1H‐detected heteronuclear multiple quantum coherence and 1H‐detected heteronuclear multiple‐bond connectivity two‐dimensional NMR experiments. Copyright © 1990 John Wiley & Sons, Ltd.