Crataegusins A and B, New Flavanocoumarins from the Dried Fruits of Crataegus pinnatifida var. major (Rosaceae)

Abstract

Crataegusins A (1) and B (2), new flavanocoumarins, were isolated from the crude drug Crataegus Fructus, i.e., the dried fruits of Crataegus pinnatifida var. major. Their structures were determined by spectroscopic methods. They were unique in terms of carrying a 3-(or 4-)substituted coumarin substructure while a flavanocoumarin generally does not carry any substituents in the 2-pyron ring. They showed a significant DPPH reducing activity compared with epicatechin. Their production would be biosynthetically regulated considering the results of an LC-MS analysis of the dried and fresh fruits, fruit skin, hypanthia, and leaves. Their structures led the authors to consider a hypothetical general biosynthetic pathway of the flavanocoumarins, to which a flavan-3-ol is converted through a Michael addition and successive oxidative decarboxylation or dehydration pathway.