The novel structure of hunterioside, the first example of monoterpenoid indole alkaloids carrying a disaccharide, was confirmed by chemical synthesis starting from tryptamine, secologanin, and a newly-developed gulucosyl donor, which selectively gives alpha-gluco type glycosidic linkage in the reaction with a secologanin derivative. (C) 1999 Elsevier Science Ltd. All rights reserved.