Two new serratene triterpenes from club moss cultivars.

Two new serratene triterpenes, 14α,21ß-dihydroxyserrat-3ß-yl acetate and 3α,21ß-dihydroxyserrat-14-en-23-oic acid, together with eight known compounds were isolated from two club moss cultivars, Phlegmariurus carinatus (Desv.) Ching and Phlegmariurus nummulariifolius (Blume) Ching. 14α,21ß-Ddihydroxyserrat-3ß-yl acetate (1) was isolated from P. carinatus, and 3α,21ß-dihydroxyserrat-14-en-23-oic acid (2), an undescribed carboxylic group at C-23 position of the serratene triterpenoids, was isolated from P. nummulariifolius. The structures of these new compounds were elucidated by using HR-ESIMS, UV, IR, 1D (1H and 13C NMR spectra), 2D NMR spectra, experimental ECD spectrometry and the single-crystal X-ray analysis. Biological evaluation of 14α,21ß-dihydroxyserrat-3ß-yl acetate (1) and lycoclavanol (8) revealed moderate cytotoxic activity on three tumor cell lines (HepG2, A549 and HuCCA-1) whereas 3α,21ß-dihydroxyserrat-14-en-23-oic acid (2) showed strong inhibitory effect on HuCCA-1 cells with the IC50 of 4.72 µM.

Phlegcarines A-C, three Lycopodium alkaloids from Phlegmariurus carinatus (Desv. ex Poir.) Ching.

Three undescribed Lycopodium alkaloids, phlegcarines A-C, along with nine known alkaloids, were isolated from the aerial parts of a gardening clubmoss Phlegmariurus carinatus (Desv. ex Poir.) Ching. Phlegcarine A is an undescribed Lycopodium alkaloid possessing an unprecedented 5/9/6/6 fused-tetracyclic ring system consisting of an oxa-cyclononanone, a piperidine, a methylcyclohaxane and an oxazolidine. Phlegcarine B is the first N-chloromethyl piperidinium Lycopodium alkaloid of (+)-lycoflexine. The semi-synthesis of phlegcarine B was investigated from (+)-fawcettimine. Phlegcarine C, an undescribed epimer of 12-epilycodoline, is a rare lycopodine-type alkaloid with ß-oriented H-4. Transformation of phlegcarine C and lycodoline to 12-epilycopodine N-oxide via keto-enol tautomerization was investigated using m-CPBA. The structural assignments were established through comprehensive spectroscopic techniques and chemical correlations. Phlegcarines A-C were assayed for their anti-acetylcholinesterase activity, but none of them exhibited biological activity more potent than that of huperzine A.

Three Lycopodium alkaloids from Thai club mosses.

Phytochemical constituents in alkaloid extracts from three Thai club mosses Huperzia squarrosa, Huperzia phlegmaria and Phlegmariurus nummularifolius were investigated. Squarrosinoxide was an undescribed Lycopodium alkaloid from H. squarrosa possessing an unprecedented 6/5/7 tricyclic spiro system. Acetyllycophlegmarianol was an undescribed N-oxide lycopodine-type alkaloid isolated from H. phlegmaria. 4-Epilycopodine, an undescribed epimer of lycopodine, was first isolated from P. nummularifolius. The structural assignments were established through comprehensive spectroscopic techniques and chemical correlations. All compounds were assayed for their anti-acetylcholinesterase activity in vitro.