Unusual ent-atisane type diterpenoids with 2-oxopropyl skeleton from the roots of Euphorbia ebracteolata and their antiviral activity against human rhinovirus 3 and enterovirus 71

Two novel ent-atisane type diterpenoids possessing the extra unusal 2-oxopropyl moiety (1 and 2) and four known analogues have been isolated from the roots of Euphorbia ebracteolata. The structures and absolute configurations of these compounds were determined by extensive spectroscopic data analysis, including 2D NMR, single-crystal X-ray crystallography, ¹³C NMR calculation, and electronic circular dichroism spectra calculation. Compounds 1 and 2 are the first examples of natural products with ent-atisane type diterpenoids possessing 2-oxopropyl skeleton. Compounds 2, 3, 5, and 6 show antiviral activities against human rhinovirus 3, with IC₅₀ values of 25.27–90.35 μM. Compounds 5 and 6 showed moderate antiviral activities against EV71 at a concentration of 100 μM.     

疏花毛萼香茶菜的二萜成分

从疏花毛萼香茶菜叶的乙醚提取物中一共分得七个二萜化合物,其中四个经各项光谱数据证明它们分别为毛萼乙素(1),毛萼晶甲(2),毛萼晶乙(3)和冬凌草素(4)。     

异叶三宝木的二萜成分及抗菌活性研究

为研究异叶三宝木(Trigonostemon heterophyllus)的二萜成分及其抗菌活性,采用硅胶柱层析、凝胶柱层析、高效液相色谱对萃取物进行分离纯化,结合现代波谱技术对所得化合物进行结构鉴定,并通过牛津杯法和2倍稀释法检测化合物对革兰氏阴性菌大肠杆菌(Escherichia coli)以及革兰氏阳性菌肺炎双球菌(Pneumococcus)的生长抑制活性和MIC值。从异叶三宝木中分离得到了6个化合物,包括5个二萜类, 1个木脂素类,分别鉴定为trigonochinene E (1)、neoboutomannin (2)、6,9-O- dedimethyltrigonostemone (3)、stelltian B (4)、3,4-secosonderianol (5)、biondinin A (6)。化合物1、2、3、5对大肠杆菌有抑制作用,MIC值分别为9.375、18.75、18.75、18.75 μg/mL。化合物2、3、4、6为首次从该种植物中分离得到,化合物4为首次从该属植物中分离得到。除化合物4外,其他化合物都有一定的抗菌活性,且化合物1、2、3对大肠杆菌抑制作用强于阳性对照硫酸卡那霉素。     

Pierisformotoxins A – D,Polyesterified Grayanane Diterpenoids from Pieris formosa and Their cAMP‐Decreasing Activities

Four highly acylated diterpenoids, designated as pierisformotoxins A–D ( 1 – 4 , resp.), along with 26 known compounds, were isolated from the flowers of Pieris formosa. Among them, pierisformotoxins A and B ( 1 and 2 , resp.) were new highly acylated grayanane diterpenoids, of which the five‐membered ring A has undergone an oxidative cleavage between C(3) and C(4), followed by lactonization, to give rise to a five‐membered lactone ring between C(3) and C(5), differing from the previously reported grayanane diterpenoids with a 5/7/6/5 ring system. Results of the cAMP‐regulation‐activity assay showed that pierisformotoxin C ( 3 ) at 10 μM (inhibitory ratio (IR): 10.1%) or 2 μM (9.8%), and pierisformotoxin B ( 2 ) at 50 μM (13.9%) significantly decreased the cAMP level in N1E‐115 neuroblastoma cells (p<0.05).     

A new metabolite with a new substitution pattern from the seeds of the Chinese Yew, Taxus mairei

A new taxoid metabolite with a new substitution pattern was isolated from the methanol extract of the seeds of Taxus mairei, and its structure was established as 5alpha,15-dihydroxy-7beta,9alpha-diacetoxy-11(15-->1)abeo-taxa-4(20),11-dien-13-one (1) on the basis of spectral analysis including (1)H- and (13)C-NMR, HMQC, HMBC, NOESY, and confirmed by HR-FAB mass spectrometry.     

Isolation and chemical modification of clerodane diterpenoids from Salvia species as potential agonists at the kappa-opioid receptor

The clerodane diterpenoid salvinorin A (1), the main active component of the psychotropic herb Salvia divinorum, has been reported to be a potent agonist at the kappa-opioid receptor. Computer modeling suggested that splendidin (2) from S. splendens, as well as related compounds, might possess similar activities. In the present study, this hypothesis was tested by determination of the binding properties of a series of structural congeners, compounds 2-8, at the mu-, delta-, and kappa-opioid receptors. However, none of these compounds showed significant binding to any of the opioid-receptor subtypes, thus disproving the above hypothesis. The novel compounds 7 and 8 were obtained semi-synthetically by selective modification of salvifarin (5), isolated from Salvia farinacea, upon epoxide-ring opening with AcOH in the presence of indium(III) triflate. Also, the X-ray crystal structure of salvifaricin (6; Fig.), obtained from S. farinacea, was determined for the first time and used, in combination with in-depth NMR experiments, to elucidate the absolute configurations of the new products. Our experiments demonstrate that the relatively well-accessible diterpenoid 6 could be used as starting material for future studies into the structure-activity relationship at the kappa-opioid receptor.     

Labdane diterpenoid glycosides from Aster veitchianus

Four new labdane-type rhamnopyranosides derived from 13-epimanool, compounds 1-4, with differently acetylated sugar moieties, were isolated from A. veitchianus. Their structures and absolute configurations were elucidated by chemical transformation, spectroscopic and mass-spectrometric analyses (IR, 1D- and 2D-NMR, HR-ESI-MS), as well as by single-crystal X-ray diffraction (compound 1). The isolates 2-4 were investigated for their cytotoxic properties against cultured human hepatoma (SMMC-7721), ovarian neoplasm (HO-8910), and leukemia (HL-60) cells, and for their antibacterial activities against Escherichia coli, Bacillus subtilis, and Staphylococcus aureus.     

Three acylated flavone glycosides from Sideritis ozturkii Aytac & Aksoy

From the aerial parts of Sideritis ozturkii, three new flavonoids, chrysoeriol 7-O-[2'-O-caffeoyl-O-acetyl-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranoside], chrysoeriol 7-O[2'-O-caffeoyl-beta-D-glucopyranosyl-(1 -->2)-beta-D-glucopyranoside] and chrysoeriol 7-O[2'-O-p-coumaroyl-6'-beta-O-acetyl-D-glucopyranosyl-(1-->2)-beta-D-glucopyranoside] named as ozturkosides A, B and C, respectively, were isolated, along with three known phenylethanoid glycosides, verbascoside, leucoseptoside A, martynoside and five known diterpenoids, 7-epicandicandiol, linearol, sidol, sideroxol, epoxyisolinearol. The structures were elucidated mainly by spectroscopic methods.     

Biotransformation of ent-13-epi-manoyl oxides difunctionalized at C-3 and C-12 by filamentous fungi

Biotransformation of ent-3beta,12alpha-dihydroxy-13-epi-manoyl oxide with Fusarium moniliforme gave the regioselective oxidation of the hydroxyl group at C-3 and the ent-7beta-hydroxylation. The action of Gliocladium roseum in the 3,12-diketoderivative originated monohydroxylations at C-1 and C-7, both by the ent-beta face, while Rhizopus nigricans produced hydroxylation at C-7 or C-18, epoxidation of the double bond, reduction of the keto group at C-3, and combined actions as biohydroxylation at C-2/epoxidation of the double bond and hydroxylation at C-7/reduction of the keto group at C-3. In the ent-3-hydroxy-12-keto epimers, G. roseum originated monohydroxylations at C-1 and C-7 and R. nigricans originated the oxidation at C-3 as a major transformation, epoxidation of double bond and hydroxylation at C-2. Finally, in the ent-3beta-hydroxy epimer R. nigricans also originated minor hydroxylations at C-1, C-6, C-7 and C-20 and F. moniliforme produced an hydroxylation at C-7 and a dihydroxylation at C-7/C-11.