From cell suspension cultures of Rauwolfia serpentina grown in an optimized production medium for the glucoalkaloid raucaffricine, a novel glucoalkaloid was isolated and identified as 17-0-acetyl-21-0-ß-D-glucopyranosyl-ajmaline (acetylrauglucine). This alkaloid is formed in very small amounts (< 5 x 10~4%). The biogenetically related Nα-demethylated base (acetyl-nor-rauglucine) and the deacetyl product rauglucine have also been detected in culture extracts. In addition 21(.R)-(ß-D-glucopyranosyl)-hydroxy-sarpagan-17-al has been isolated and identified as an artifact which originates from raucaffricine. © 1988, Walter de Gruyter. All rights reserved.