Patavine, a New Arylnaphthalene Lignan Glycoside from Shoot Cultures of Haplophyllum patavinum.

Abstract

In a number of recent reports, 1-3) we described the structures and distributions in vivo and in vitro of different secondary metabolite classes as coumarins, alkaloids, and lignans produced by Haplophyllum patavinum (L.) G. DON fil. (Rutaceae), the only species of this genus growing in Italy in a very small disjointed range on the Euganean Hills (Padova, Italy). In the course of the establishment of a protocol for the regeneration of this endangered plant, 4) the biosynthetic capabilities of shoot cultures were also evaluated. In a previous report we identified furoquinoline and quinolone alkaloids from shoot cultures. 3)We now report the isolation from MeOH extract shoot cultures of a new arylnaphthalene lignan glycoside, patavine (1), together with five known lignans. The known compounds 2-6 were identified as justicidin B (2), diphyllin (3), tuberculatin (4), majidine (5), and arabelline (6) by comparison of their spectral data with those of previously reported data. [5][6][7][8][9] These known compounds were also detected in the native plants of this species.2) Compound 1, obtained as an yellowish amorphous powder, presented a UV maximum absorption spectrum and a bluish fluorescence under UV light similar to lignans 2-6 indicating an arylnaphthalene nucleus.10) Its molecular formula (C 36 H 40 O 19 ) was determined by 1 H-and 13 C-NMR analyses, and (high resolution) electrospray ionization mass spectroscopy ((HR)-ESI-MS), which gave a molecular adduct [MϩNa] ϩ at m/z 799.2752 and fragments at m/z 645 and 381 due to the cleavage of one and three pentose units, respectively. In the 1 H-and 13 C-NMR spectra, typical signals due to the arylnaphthalene lignan, diphyllin (3), were observed 9) along with signals due to a sugar portion (Table 1). The structure of the oligosaccharide unit was determined by one-dimensional total correlation spectroscopy (1D-TOCSY) and two-dimensional (2D)-NMR experiments. The A new arylnaphthalene lignan glycoside, patavine (1), together with five known lignans, justicidin B (2), diphyllin (3), tuberculatin (4), majidine (5), and arabelline (6) were isolated from shoot cultures of Haplophyllum patavinum. The structure of the new compound was elucidated by extensive one-dimensional (1D) and two-dimensional (2D) NMR experiments and mass spectrometry. The cytotoxicity of compounds 1, and 3-6 against LoVo human colon carcinoma cells was investigated.

Potent Cytotoxic Arylnaphthalene Lignan Lactones from Phyllanthus poilanei

“…Mananthes patentiflora ), 10,11 and J. procumbens ; 12−14 the Lamiaceae, from Hyptis verticillata ; 15 the Linaceae, from Linum leonii ; 16 the Myristicaceae, from Knema furfuracea ; 17 the Phyllanthaceae, from Cleistanthus collinus , 18 Phyllanthus acutissima , 19 P. myrtifolius , 20,21 P. oligospermus , 22 P. piscatorum , 23 and P. taxodiifolius ; 24 and the Rutaceae, from Haplophyllum cappadocicum , 25 H. buxbaumii , 26,27 H. dauricum , 28 and H. patavinum . 29 …”

Complete assignments of 1H and 13C NMR data for three new arylnaphthalene lignan from Justicia procumbens

“…Compounds 4-6 were identified as justicidinoside B, justicidinoside C, [4] and diphyllin-1-O-β-D-apiofuranoside, [14] respectively, by comparison of their NMR spectral data ( 1 H and 13 C) with published data.…”

Reversal of P-Glycoprotein-Mediated Drug Efflux by Eudesmin from Haplophyllum perforatum and Cytotoxicity Pattern versus Diphyllin, Podophyllotoxin and Etoposide

“…Its anti-tumour effects have been attributed to inhibition of DNA synthesis, cell-cycle blockade, induction of apoptosis and, down-regulation of matrix metalloproteinase-9 activity [16], [17]. Biologically active diphyllin glycosides have also been extracted from Justicia procumbens [18] and from certain Haplophyllum species [19] or derived-shoot cultures [20]. Yet, the value of diphyllin as raw material for the hemisynthesis of anticancer drugs is very limited.…”