Chlorophyll Catabolites in Fall Leaves of the Wych Elm Tree Present a Novel Glycosylation Motif

Fall leaves of the common wych elm tree (Ulmus glabra) were studied with respect to chlorophyll catabolites. Over a dozen colorless, non-fluorescent chlorophyll catabolites (NCCs) and several yellow chlorophyll catabolites (YCCs) were identified tentatively. Three NCC fractions were isolated and their structures were characterized by spectroscopic means. Two of these, Ug-NCC-27 and Ug-NCC-43, carried a glucopyranosyl appendage. Ug-NCC-53, the least polar of these NCCs, was identified as the formal product of an intramolecular esterification of the propionate and primary glucopyranosyl hydroxyl groups of Ug-NCC-43. Thus, the glucopyranose moiety and three of the pyrrole units of Ug-NCC-53 span a 20-membered ring, installing a bicyclo[17.3.1]glycoside moiety. This structural motif is unprecedented in heterocyclic natural products, according to a thorough literature search. The remarkable, three-dimensional bicyclo[17.3.1]glycoside architecture reduces the flexibility of the linear tetrapyrrole. This feature of Ug-NCC-53 is intriguing, considering the diverse biological effects of known bicyclo[n.3.1]glycosidic natural products.