Dereplication of tropane alkaloids from four Erythroxylum species using liquid chromatography coupled with ESI‐MSn and HRESIMS

Abstract

RationaleTropane alkaloids represent an important class of secondary metabolites, but many of these compounds are already described in the scientific literature, so the use of guided identification and isolation strategies, such as dereplication, represent a fast and safe alternative.MethodsFor the annotation of the tropane alkaloids the chloroform phases of the four Erythroxylum species were analyzed by high‐performance liquid chromatography coupled to mass spectrometry with positive‐mode electrospray ionization, then the ions of their protonated molecules, molecular formulas and fragmentation patterns were observed and a comparison of the obtained data with those present in the scientific literature was performed. The compounds not fully annotated were isolated and characterized by 1H and 13C nuclear magnetic resonance spectroscopy.ResultsThe annotation of 29 tropane alkaloids was performed, some being described for the first time in the family Erythroxylaceae. The chemical profiles of these secondary metabolites in the four Erythroxylum species analyzed were traced and compared. Isolation of three compounds whose mass spectral data were not sufficient for their full annotation was performed. They were 6‐(benzoyloxy)‐3‐(3,5‐dimethoxy‐4‐hydroxybenzoyloxy)tropane, 6‐(benzoyloxy)‐3‐(3,4,5‐trimethoxybenzoyloxy)tropane and 6‐(benzoyloxy)‐3‐(3,4,5‐trimethoxycinamoyloxy)tropane, first reported in the species Erythroxylum revolutum Mart.ConclusionsThis work contributes to the phytochemical knowledge of the genus Erythroxylum, and demonstrates the efficiency and importance of using guided isolation methodologies of secondary metabolites in natural products research. Since safe results were presented in the annotation of the compounds evidenced, employing small quantities of organic solvents, when compared to classical methodologies, besides promoting an optimization in the research time.