DETERMINATION OF THE STRUCTURE OF FUSAPROLIFERIN BY H-1-NMR AND DISTANCE GEOMETRY

The absolute configuration of fusaproliferin, a toxic metabolite produced by Fusarium proliferatum, was determined by the combined use of H-1 NMR and distance geometry. The configuration of double bonds has been determined in agreement with NOESY buildup data. An R configuration for C10 was determined using Mosher's method. Processing the constraints obtained from NOESY experiments with a distance geometry program, a limited number (80) of possible structures was derived. An agglomerative nonhierarchical method of clustering was used in order to place these structures into classes suggested by the data, and not previously defined in any way. This statistical method showed that indeed the structures could be grouped in four classes. One of these classes is represented by a single structure, with the highest sum of violations and was discarded. All other structures have the same chirality; respectively S for C14 and R for C15. In solution the overall conformation is quite well defined in the region of the five-member ring and the planes of double bonds C2-C3 and C11-C12, while near to C8 and C9 internal flexibility appears evident.