•The first total synthesis of similisines A, B and stereoisomers was accomplished.•The synthesis avoided any protecting-group manipulations.•The key spirocenter was constructed via intramolecular Friedel-Crafts cyclization.•The cytotoxic and NO inhibitory activities of synthetic compounds were discussed.The first total synthesis of similisines A and B, a pair of unprecedented polybrominated spiro-trisindole enantiomers isolated from Laurencia similis, and their all stereoisomers had been accomplished in 6 steps from the known 5,6-dibromoindole. The described synthesis avoided any protecting-group manipulations, and the key all-carbon spirocenters were constructed via an intramolecular Friedel-Crafts cyclization. In addition, the rotamers of similisines and cytotoxic and NO production inhibitory activities of synthetic compounds were also discussed.Download high-res image (104KB)Download full-size image

Three new sesquiterpene glycosides (1–3), three new glycerol glycosides (4–6), two new alkaloids (7–8), together with seven known compounds (9–15) all of which were isolated from the genus Pilea for the first time, were isolated from the whole plants of Pilea cavaleriei Levl subsp. cavaleriei. Their structures were determined by extensive spectroscopic techniques and chemical methods. The cytotoxic activity of the isolated compounds was evaluated against four cancer cell lines, and none of the tested compounds caused a significant reduction of the cell number.Download high-res image (120KB)Download full-size image

Two new oplopane sesquiterpenes, gmelinin A (1) and gmelinin B (2), were isolated from Artemisia gmelinii Web. ex Stechm. Their structures were established by spectroscopic techniques (mainly 1D and 2D NMR) and application of the modified Mosher method.Two new oplopane sesquiterpenes, gmelinin A (1) and gmelinin B (2), were isolated from Artemisia gmelinii Web. ex Stechm.

A phytochemical investigation of the roots of Symplocos caudata Wall (Symplocaceae) resulted in isolation and characterization of four optical isomers of a neolignan glycoside (1–4), a lignan lactone glycoside (5), a phenylpropanoid glycoside (6), as well as two known compounds (7, 8). Their structures were elucidated as (7S,8S)-threo-7,9,9′-trihydroxy-3,3′-dimethoxy-8-O-4′-neolignan-4-O-β-d-glucopyranoside (1), (7R,8R)-threo-7,9,9′-trihydroxy-3,3′-dimethoxy-8-O-4′-neolignan-4-O-β-d-glucopyranoside (2), (7R,8S)-erythro-7,9,9′-trihydroxy-3,3′-dimethoxy-8-O-4′-neolignan-4-O-β-d-glucopyranoside (3), (7S,8R)-erythro-7,9,9′-trihydroxy-3,3′-dimethoxy-8-O-4′-neolignan-4-O-β-d-glucopyranoside (4), 8R,8′R-matairesinol-4-O-β-d-xylopyranosyl-(1 → 2)-O-β-d-glucopyranoside (5), 1-O-[β-d-xylopyranosyl-(1 → 6)-O-β-d-glucopyranosyl]-2,6-dimethoxy-4-propenyl-phenol (6), matairesinoside (7), and (R)-1-O-(β-d-glucopyranosyl)-2-[2-methoxy-4-(ω-hydroxypropyl)-phenoxyl]-propan-3-ol (8) on the basis of spectroscopic data (1D and 2D NMR, MS and CD) and chemical evidence.Four optical isomers of 7,9,9′-trihydroxy-3,3′-dimethoxy-8-O-4′-neolignan-4-O-β-d-glucopyranoside, a lignan lactone glycoside, and a phenylpropanoid glycoside were isolated from Symplocos caudata

•Drostanolone metabolic profile was first investigated by LC–QTOFMS.•Sulfate-conjugated metabolites were first reported for drostanolone.•New potential biomarkers S4 and G1 were confirmed for drostanolone.•Direct analysis of intact metabolites was first reported.•Eleven urinary metabolites were characterized and identified.Drostanolone is one of the most frequently detected anabolic androgenic steroids in doping control analysis. Here, we studied drostanolone urinary metabolic profiles using liquid chromatography quadruple time of flight mass spectrometry (LC–QTOF-MS) in full scan and targeted MS/MS modes with accurate mass measurement. The drug was administered to one healthy male volunteer and liquid–liquid extraction along with direct-injection were used to analyze urine samples. Chromatographic peaks for potential metabolites were identified with the theoretical [M−H]− as a target ion in a full scan experiment and actual deprotonated ions were analyzed in targeted MS/MS mode. Eleven metabolites including five new sulfates, five glucuronide conjugates, and one free metabolite were confirmed for drostanolone. Due to the absence of useful fragment ions to illustrate the steroid ring structure of drostanolone phase II metabolites, gas chromatography mass spectrometry (GC–MS) was used to obtain structural details of the trimethylsilylated phase I metabolite released after enzymatic hydrolysis and a potential structure was proposed using a combined MS approach. Metabolite detection times were recorded and S4 (2α-methyl-5α-androstan-17-one-6β-ol-3α-sulfate) and G1 (2α-methyl-5α-androstan-17-one-3α-glucuronide) were thought to be new potential biomarkers for drostanolone misuse which can be detected up to 24 days by liquid–liquid extraction and 7 days by direct-injection analysis after intramuscular injection. S4 and G1 were also detected in two drostanolone-positive routine urine samples.Download full-size image