Chemotaxonomy of the pantropical genus Merremia (Convolvulaceae) based on the distribution of tropane alkaloids

• Published in: Phytochemistry (Oxford) Vol. 66; no. 12; pp. 1448 - 1464
• Main Authors: Jenett-Siems, Kristina, Weigl, Robert, Böhm, Anke, Mann, Petra, Tofern-Reblin, Britta, Ott, Sonja C., Ghomian, Azar, Kaloga, Maki, Siems, Karsten, Witte, Ludger, Hilker, Monika, Müller, Frank, Eich, Eckart
• Format: Journal Article
• Language: English
• Published: OXFORD Elsevier Ltd 01.06.2005; Elsevier
• Subjects: 3alpha-acyloxytropane; 3alpha-benzoyloxytropane; 3alpha-nicotinoyloxytropane; 4'-dihydroconsabatine; Alkaloids - classification; Alkaloids - isolation & purification; Biochemistry & Molecular Biology; Biological and medical sciences; Chemical constitution; Chemotaxonomy; Classification; Concneorine; Convolvulaceae; Convolvulaceae - chemistry; Convolvulaceae - classification; Fundamental and applied biological sciences. Psychology; Gas Chromatography-Mass Spectrometry; GC–MS; Life Sciences & Biomedicine; Merredissine; Merremia; Merremieae; Merresectines; methylpseudoecgonine; Molecular Structure; N-methylpyrrolidinylhygrines; Nicotine; phytochemicals; Plant cytology, morphology, systematics, chorology and evolution; plant extracts; Plant Extracts - isolation & purification; Plant physiology and development; Plant Roots - chemistry; Plant Sciences; plant taxonomy; Pyrrolidine alkaloids; Pyrrolidines - classification; Pyrrolidines - isolation & purification; Science & Technology; spectral analysis; Spermatophyta; Structure elucidation; Systematics (diagnosis, chromosome numbers); Tropane alkaloids; Tropanes - classification; Tropanes - isolation & purification; GC–MS; Concneorine; Merresectines; Chemotaxonomy; Convolvulaceae; Merremieae; 4′-Dihydroconsabatine; Pyrrolidine alkaloids; Merremia; Merredissine; Structure elucidation; Tropane alkaloids; Nicotine; 4'-dihydroconsabatine; nicotine; tropane alkaloids; ACID; merredissine; LEAVES; TUBEROSA; merresectines; chemotaxonomy; GC-MS; pyrrolidine alkaloids; TRANSFORMED ROOT CULTURES; COA; RESIN-GLYCOSIDES; BIOSYNTHESIS; concneorine; structure elucidation; DISSECTA; Molecular structure; Taxonomy; Pyrrolidine derivatives; Alkaloid; Dicotyledones; Angiospermae; Root; 4'-Dihydroconsabatine; Glucoside; Tropane derivatives; Position isomer; Isolation; Spermatophyta; Yield
• ISSN: 0031-9422; 1873-3700
• DOI: 10.1016/j.phytochem.2005.04.027

A comprehensive GC–MS analysis of 18 spp. revealed altogether 74 tropanes and 13 pyrrolidines, respectively. Four aromatic 3α-acyloxytropanes (merresectines A–D) of chemotaxonomic relevance as well as 3α, 6β-di-(4-methoxybenzoyloxy)tropane (merredissine) have been isolated and structurally elucidated. The occurrence and distribution of tropane and biogenetically related pyrrolidine alkaloids in 18 Merremia species of paleo-, neo-, and pantropical occurrence have been studied. The extensive GC–MS study included members of almost all sections of the genus and has been carried out with epigeal vegetative parts as well as with roots. It comprises altogether 74 tropanes and 13 pyrrolidines including nicotine. Along with datumetine known already from a solanaceous species, the study led to the isolation (from M. dissecta and M. guerichii, respectively) and structure elucidation (spectral data) of four novel 3α-acyloxytropanes, merresectines A–D: 3α-(4-methoxybenzoyloxy)nortropane (A), 3α-kurameroyloxytropane (B), 3α-nervogenoyloxytropane (C), 3α-[4-(β- d-glucopyranosyloxy)-3-methoxy-5-(3-methyl-2-butenyl)benzoyloxy]tropane (β- d-glucoside of D). Moreover, the novel 3α,6β-di-(4-methoxybenzoyloxy)tropane (merredissine) has been isolated from M. dissecta and structurally elucidated. In addition the structures of datumetine and merresectine A could be confirmed by synthesis. Spectral data for two known 3α-acyloxytropanes (merresectine E β- d-glucoside, 4′-dihydroconsabatine) and one known 3β-acyloxytropane (concneorine) are documented for the first time. The structures of three further merresectines (F-H) have been determined by mass spectrometry. Furthermore, the linkage (2′,3- and 2′,4-, respectively) of two position isomer N-methylpyrrolidinylhygrines was proven by synthesis. The results of the study contribute to the solution of infrageneric taxonomic problems. Whereas all species yield pyrrolidine alkaloids without suitably differentiating results the diverging occurrence of tropane alkaloids leads to three groups of sections: (1) taxa free of tropanes, (2) taxa with simple tropanes, and (3) taxa with merresectines in addition to simple tropanes.