Bin Cong

Constituents from Salvia Species and Their Biological Activities

Yi-Bing Wu,† Zhi-Yu Ni,† Qing-Wen Shi,*,† Mei Dong,‡ Hiromasa Kiyota,* Yu-Cheng Gu,†,∥ and Bin Cong*,‡ †School of Pharmaceutical Sciences, Hebei Key Laboratory of Forensic Medicine, Hebei Medical University, Shijiazhuang, Hebei Province 050017, China ‡Department of Forensic Medicine, Hebei Medical University, Hebei Key Laboratory of Forensic Medicine, Shijiazhuang, Hebei Province 050017, China Department of Bioscience and Biotechnology for Future Bioindustry, Graduate School of Agricultural Science, Tohoku University, 1-1 Tsutsumidori-Amamiya, Aoba-ku, Sendai 981-8555, Japan Syngenta Jealott’s Hill International Research Centre, Berkshire RG42 6EY, United Kingdom

Natural Taxanes: Developments Since 1828

Natural Taxanes: Developments Since 1828 Yu-Fang Wang, Qing-Wen Shi,* Mei Dong, Hiromasa Kiyota,* Yu-Cheng Gu, and Bin Cong* School of Pharmaceutical Sciences, Hebei Medical University, Shijiazhuang, Hebei Province, 050017, China Department of Forensic Medicine, Hebei Medical University, Hebei Key Laboratory of Forensic Medicine, Shijiazhuang, Hebei Province, 050017, China Department of Bioscience and Biotechnology for Future Bioindustry, Graduate School of Agricultural Science, Tohoku University, 1-1 Tsutsumidori-Amamiya, Aoba-ku, Sendai 981-8555, Japan Syngenta Jealott’s Hill International Research Centre, Berkshire, RG42 6EY, U.K.

Echinopines A and B: sesquiterpenoids possessing an unprecedented skeleton from Echinops spinosus.

Echinopines A (1) and B (2), novel sesquiterpenoids with an unprecedented rearranged skeleton named echinopane, were isolated from the roots of Echinops spinosus. The structures were elucidated by extensive spectroscopic analysis. The relative configuration of 1 was assigned by a combination of NOESY correlations and a simulation analysis. A plausible biosynthetic pathway for echinopane was discussed.

Secondary Metabolites of Plants from the Genus Saussurea: Chemistry and Biological Activity

The Asteraceae family comprises ca. 1000 genera, mainly distributed in Asia and Europe. Saussurea DC., as the largest subgenus of this family, comprises ca. 400 species worldwide, of which ca. 300 species occur in China. Most plants in China grow wild in the alpine zone of the Qingzang Plateau and adjacent regions at elevations of 4000 m. Plants of the genus Saussurea (Asteraceae) are used in both traditional Chinese folk medicine and Tibet folklore medicine, since they are efficacious in relieving internal heat or fever, harmonizing menstruation, invigorating blood circulation, stopping bleeding, alleviating pain, increasing energy, and curing rheumatic arthritis. A large number of biologically active compounds have been isolated from this genus. This review shows the chemotaxonomy of these compounds (215 compounds) such as sesquiterpenoids (101 compounds), flavonoids (19 compounds), phytosterols (15 compounds), triterpenoids (25 compounds), lignans (32 compounds), phenolics (23 compounds), and chlorophylls (11 compounds). Biological activities (anti‐inflammatory, anticancer, antitumor, hepatoprotective, anti‐ulcer, cholagogic, immunosuppressive, spasmolytic, antimicrobial, antiparasitic, antifeedant, CNS depressant, antioxidant, etc.) of these compounds, including structure–activity relationships, are also discussed.

Achillinin A, a Cytotoxic Guaianolide from the Flower of Yarrow, Achillea millefolium

Achillinin A (2β,3β-epoxy-1α,4β,10α-trihydroxyguai-11(13)-en-12,6α-olide, 1), a new guaianolide isolated from the flower of Achillea millefolium, exhibited potential antiproliferative activity to A549, RERF-LC-kj and QG-90 cells with 50% inhibitory concentration (IC50) values of 5.8, 10 and 0.31 μM, respectively.

Antitumour activities of sesquiterpene lactones from Inula helenium and Inula japonica.

3 Eight sesquiterpene lactones were isolated from the roots of Inula helenium and fl owers of I. japonica. Among them, isoalantolactone () and santamarine (6) exhibited significant growth inhibitory activities against gynecologic cancer cell lines, while others weakly inhibited the growth of the cell lines (IC50 ≤ 100 μM). In addition, 3 significantly inhibited the tumour growth of S180 tumour-bearing mice. Compounds 3 and 6 were not toxic to human embryonic lung fibroblast cells in vitro. These results demonstrated that the antitumour activities are closely related to the structures of the compounds, that is, an α-exomethylene- γ-lactone ring is necessary for these activities.

Taxanes from the leaves of Taxus cuspidata.

A new taxane, 13-oxobaccatin III (2), and five known taxanes, 10-deacetyl-13-oxobaccatin III (1), baccatin III (3), 7-epi-10-deacetyltaxol (4), 19-debenzoyl-19-acetyltaxinine M (5), and 5a-decinnamoyltaxagifine (6), were isolated from the leaves of the Japanese yew, Taxus cuspidate. Their structures were established on the basis of the analysis of their spectral data.

A Novel Taxane 13-Glucoside and Other Taxanes from the Leaves of Taxus cuspidata

Three new taxanes, 2 α,9 α,10 β-triacetoxy-13 α-( β-D-glucopyranosyloxy)taxa-4(20),11-dien-5 α-ol, 5 α,10 β,13 α-triacetoxytax-11-ene-2 α,7 β,9 α,20-tetraol, and 5 α,10 β,13 β-triacetoxy-2 α,7 β-dihydroxy-2(3→20) abeotaxa-4(20),11-dien-9-one, were isolated from the leaves of the Japanese yew, Taxus cuspidata. Compound 1 is the first example of a taxane with 13-glycosidic linkage.

Xylomexicanins A and B, new Δ14,15-mexicanolides from seeds of the Chinese mangrove Xylocarpus granatum.

Two new mexicanolide-type limonoids, named xylomexicanin A (1) and xylomexicanin B (2), were isolated from seeds of the Chinese mangrove Xylocarpus granatum. Their structures were elucidated on the basis of spectroscopic methods. Compound 1 exhibited antiproliferative activity against human breast carcinoma cells (KT), while 2 did not show inhibitory effects on eleven human tumour cell lines tested.

Triterpenoids and Steroids from the Leaves of Forsythia suspensa

Forsythia suspensa (Thunb.) Vahl is a deciduous shrub of the Oleaceae family, which is widely distributed in China, North and South Korea, and Japan. Its fruits, “Lian qiao”, have been used for treating conditions such as gonorrhea, erysipelas, inflammation, pharyngitis, pyrexia, tonsillitis, and ulcers in Chinese and Japanese medicine [1]. The immature leaves of this plant have been used as a health tea by residents of longevity villages in Wuan, Hebei Province and Pingding, Shanxi Province in China [2]. In recent years, studies have shown that the F. suspensa leaf extract has a variety of pharmacological activities, such as antioxidant, hepatoprotective, anti-aging, and cardioprotective [3]. However, its chemical constituents have not been thoroughly investigated, and only (+)-pinoresinol, (–)-pinoresinol, and phillygenin (lignans), forsythiaside (phenylpropanoid), quercetin and rutin (flavonoids), and ursolic acid (triterpenoid) have been reported [4–6]. The leaves of F. suspensa were collected in October 2009 from the Dongyangpo production base, Jingxing County, Hebei Province, and identified by Prof. Jianhua Wang, Pharmacognosy Laboratory, School of Pharmaceutical Sciences, Hebei Medical University. Chemical investigation of the ethanol extract of Forsythia suspensa led to the isolation of ten compounds (1–10). Dried F. suspensa leaves (4.4 kg) were extracted with 95% ethanol at room temperature. After evaporation of the solvent under reduced pressure, the residue was suspended in water and extracted with petroleum ether, CH2Cl2, EtOAc, and n-BuOH, successively. The CH2Cl2 fraction (288.6 g) was subjected to silica gel column chromatography, eluting with petroleum ether–CH3COCH3 (10:1 1:1). Fraction 1 afforded 1 (33.3 mg). Fraction 9 was subjected to repeated chromatography to obtain 5 (20.0 mg). Fraction 10 was chromatographed on silica gel, eluting with CH2Cl2–CH3COCH3 (80:1 1:1) to yield 6 (30.1 mg), 3 (8.9 mg), and 8 (306.5 mg). The petroleum ether fraction (194.1 g) was subjected to silica gel column chromatography, eluting with CH2Cl2–EtOAc (50:1 1:1). Fraction 1 was subjected to a silica gel column, eluting with petroleum ether–CH3COCH3 (10:1 2:1) to afford 4 (15.5 mg), 9 (3.1 mg), and 10 (231.6 mg). Fraction 2 afforded 7 (10.3 mg) and fraction 5 afforded 2 (7.8 mg). Their chemical structures were identified by NMR spectroscopy and were determined to be 3 -acetoxy-11-en-olean28,13-olide (1) [7], 3 -acetoxyolean-12-en-28-oic acid (2) [8], 3 -hydroxy-11-oxo-olean-12-en-28-oic acid (3) [9], 3 -acetoxyurs-12-en-28-oic acid (4) [10], 2 ,3 -hydroxyursolic acid (5) [11], ursolic acid (6) [12], betulin (7) [13], alphitolic acid (8) [7], stigmast-4-en-3-one (9) [14], and -sitosterol (10) [15] by comparing the data with those in the literature. Compounds 8 and 10 are reported in the leaves of this plant for the first time; the other compounds except 6 were isolated from the Forsythia genus for the first time. As some of the 1H and 13C NMR data had been incorrectly assigned for 3 -acetoxyolean12-en-28-oic acid (2) and alphitolic acid (8) due to NMR limitations, in particular no access to 2D NMR, in the original reported papers, all the 1H and 13C NMR spectral data of these two compounds were reassigned after interpretation of their 2D NMR spectroscopic data.