New phlegmarane-type, cernuane-type, and quinolizidine alkaloids from two species of Lycopodium

Complanadine B, obscurumines A and B, new alkaloids from two species of Lycopodium

“…4 In recent ten years, much efforts have been devoted to preparation of structurally simplified analogues and derivatives with the tricyclic skeleton of huperzine A as a promising lead compound of acetylcholinesterase inhibitors. 5 Recently, we have isolated some new types of alkaloids from extracts of the genus Lycopodium collected in Japan, [6][7][8][9][10][11][12][13][14] and biomimetic transformation through a modified Polonovski reaction has been examined. 15 With an aim to isolate structurally interesting alkaloids and key intermediates to clarify the biogenetic pathway, purification of extracts of Lycopodium complanatum and L. obscurum (Lycopodiaceae) led to isolate three new alkaloids, complanadine B (1) from L. complanatum, and obscurumines A (2) and B (3) from L. obscurum.…”

“…13 C NMR Data of obscurumines A (2) and B(3) in CDCl 3 at 300 K Overlapped with solvent signals. measurements of FABMS, and Mr. N. Yoshida, Health Sciences University of Hokkaido, for the botanical identification.…”

Malycorins A-C, New Lycopodium Alkaloids from Lycopodium phlegmaria

“…9,10) Recently we isolated new types of alkaloids such as sieboldine A, 11) serratezomine A, 12) complanadine A, 13) lyconadin A, 14) senepodine A, 15,16) lyconesidine A, 17) himeradine A, 18) cermizine A, 19) and nankakurine A 20,21) from various Lycopodium spp. Our interest has been focused on isolation of structurally interesting alkaloids and biosynthetic intermediates to clarify the biogenetic pathway.…”

A concise synthesis of the Lycopodium alkaloid cermizine D

“…Along with cermizines A-C (Figure 1), cermizine D was isolated and structurally elucidated in 2004, by Kobayashi and collaborators from the club mosses Lycopodium cernuum and Lycopodium chinense. 1 The same group performed bioactivity studies and reported that cermizine D (1) exhibited citotoxicity against murine lymphoma L1210 cells, with a IC50 of 7.5 µg/mL (30 µM). Interestingly, before the isolation of cermizine D in 2003, two diastereomers of the natural product 2 and 3 were synthesized (Figure 2) by Ayer 3 in 1967, and by Ban 4 in 1975, while both groups were pursuing the synthesis of dihydrodeoxyepiallocernuine (4).…”

“…A Wittig olefination followed by two consecutive hydrogenations would complete the synthesis of cermizine D (1). The known bicyclic dihydropyridone 6 was prepared in two steps (Scheme 2).…”