Lycoflexine, a new type of lycopodium alkaloid

Tetrahedron Letters
1973.0

Abstract

Examination of the alkaloids obtained by methanol extraction of Lycopodium clavatum var. inflexum collected in the Eastern Transvaal resulted in the isolation of five alkaloids: four known C16 compounds (lycopodine, dihydrolycopodine, lycodoline, fawcettimine) and a new C17 compound named lycoflexine, which possesses a carbon-nitrogen skeleton differing from previously reported alkaloids in this group. Lycoflexine (C17H25NO2) was characterized via spectral data (IR showing carbonyl absorption at 1740 and 1695 cm⁻¹, active methylene at 1410 cm⁻¹; NMR revealing a secondary C-methyl group and no olefinic protons; MS with parent peak at m/e 275 and base peak at m/e 84) and X-ray crystallography (lycoflexine hydrobromide, monoclinic space group P2₁, R-factor 9.7%), confirming a tetracyclic structure. Its absolute stereochemistry was established using a chiroptical method (CD spectra). Lycoflexine differs from fawcettimine by a methylene bridge linking nitrogen and C-4, and can be synthesized from fawcettimine via an intramolecular Mannich reaction with formaldehyde (ca. 50% yield). Experiments (extraction with 5% aq. HCl, negligible formaldehyde in extracts, detection in plant ether extract) confirmed lycoflexine is a natural alkaloid present in the plant.

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