C₁₄-Polyacetylene glucosides from <i>Codonopsis pilosula</i>

<div><p>Seven new C₁₄-polyacetylene glucosides codonopilodiynosides A–G (<b>1</b>–<b>7</b>) were isolated from an aqueous extract of the <i>Codonopsis pilosula</i> roots. Their structures were determined by spectroscopic and chemical methods as (–)-(5<i>S</i>,6<i>E</i>,12<i>E</i>)-tetradeca-6,12-dien-8,10-diyn-1,5,14-triol 5-<i>O</i>-β-d-glucopyranoside (<b>1</b>), (–)-(5<i>S</i>,6<i>E</i>,12<i>E</i>)-tetradeca-6,12-dien-8,10-diyn-1,5,14-triol 5-<i>O</i>-β-d-glucopyranosyl-(1″ → 2′)-β-d-glucopyranoside (<b>2</b>), (–)-(5<i>S</i>,6<i>E</i>,12<i>E</i>)-tetradeca-6,12-dien-8,10-diyn-1,5,14-triol 5,14-di-<i>O</i>-β-d-glucopyranoside (<b>3</b>), (–)-(5<i>S</i>,6<i>E</i>)-tetradeca-6-en-8,10-diyn-1,5,14-triol 5-<i>O</i>-β-d-glucopyranoside (<b>4</b>), (–)-(5<i>S</i>,6<i>E</i>,12<i>E</i>)-tetradeca-6,12-dien-8,10-diyn-1,5-diol 5-<i>O</i>-β-d-glucopyranosyl-(1″ → 2′)-β-d-glucopyranoside (<b>5</b>), (–)-(6<i>S</i>,4<i>E</i>,12<i>E</i>)-tetradeca-4,12-dien-8,10-diyn-1,6-diol 6-<i>O</i>-β-d-glucopyranosyl-(1″ → 2′)-β-d-glucopyranoside (<b>6</b>), and (–)-(5<i>S</i>,6<i>E</i>)-tetradeca-6-en-1,5-epoxy-8,10-diyn-14-ol 14-<i>O</i>-β-d-glucopyranosyl-(1″ → 2′)-β-d-glucopyranoside (<b>7</b>), respectively. The absolute configurations of <b>1</b>–<b>7</b> were assigned by enzymatic hydrolysis followed by isolation of glucose and aglycones (<b>1a</b> and <b>4a</b>–<b>7a</b>), and subsequent comparison of specific rotation, TLC, and ¹H NMR data of the glucose with an authentic sugar sample and application of modified Mosher's method based on the MPA determination rule of Δδ^<i>RS</i> values for <b>1a</b> and <b>4a,</b> and Δδ^<i>S</i> values for <b>6a</b>. The configuration of <b>7</b> was assigned by electronic circular dichroism calculations based on the quantum-mechanical time-dependent density functional theory.</p></div

Nitrogenous chemical constituents and their antitumor activities evaluation <i>in vitro</i> from the aerial parts of <i>Corydalis impatiens</i> (pall.) Fisch

Four new compounds, impatienines E-H (1–4), together with 18 known ones (R)-N-methylcoclaurine (5), impatienine I (6), thalifoline (7), iseluxine (8), pisoquinoline (9), corydaldine (10), northalifoline (11), noroxyhydrastinine (12), 6,7-methylenedioxy-1(2H)-isoquinolinone (13), N-methylcorydaldine (14), oxyhydrastinine (15), corypalline (16), N-trans-feruloylmethoxytyramine (17), N-trans-feruloyldopamine (18), N-trans-feruloyltyramine (19), N-trans-sinapoyltyramine (20), N-cis-feruloyltyramine (21), N-cis-sinapoyltyramine (22) were obtained from the aerial parts of Corydalis impatiens (pall.) Fisch. Their structures were elucidated by extensive spectroscopic analysis (1D- and 2D-NMR, HR-ESIMS, IR, UV) and/or comparison with reported literature. The inhibitory effects of these isolates were also evaluated against the growth of cancer cells (A549, H1299 and HepG2). Compounds 2 and 4 showed significant inhibitory effect on HepG2 cancer cells with IC50 values of 8.62, 8.32 μM, respectively (positive control cisplatin: IC50, 6.32 μM). Compounds 22 and 4 exhibited moderate inhibitory effects against A549 cancer cells, and the IC50 values were 7.78 and 12.54 μM, respectively (positive control cisplatin: IC50, 1.83 μM).</p

Polycycloiridals with a Cyclopentane Ring from <i>Iris tectorum</i>

Six new iridal-type triterpenoids containing an unprecedented cyclopentane ring, polycycloiridals E–J (<b>1</b>–<b>6</b>), were isolated from a large-scale re-extraction of <i>Iris tectorum</i>. A possible biosynthesis pathway is postulated. The known spirioiridotectal D (<b>7</b>) was also obtained in the current investigation, and its structure was unequivocally defined using X-ray diffraction data. Compound <b>7</b> suppressed LPS-activated NO production in the BV2 cell line with an IC₅₀ value of 0.54 μM

4-Hydroxybenzyl-substituted glutathione derivatives from <i>Gastrodia elata</i>

<div><p>Seven new 4-hydroxybenzyl-substituted glutathione derivatives (<b>2</b>–<b>8</b>), together with a known analogue (<b>1</b>), were isolated from the aqueous extract of <i>Gastrodia elata</i> Blume rhizomes. Their structures were determined by using spectroscopic and chemical methods. The absolute configurations of <b>1</b>–<b>8</b> were assigned by using Marfey's method, combined with comparing the NMR and CD spectroscopic data of sulfoxide moieties in <b>3</b>–<b>6</b> with those of <i>S</i>-(4-hydroxybenzyl)cysteine sulfoxide stereoisomers (<b>9</b>–<b>12</b>) synthesized as authentic samples. The configurations of <b>9</b>–<b>12</b> were confirmed by electronic CD calculations based on the quantum-mechanical time-dependent density functional theory. Furthermore, the structures of <b>1</b>, <b>3</b>, <b>5</b>, <b>7</b>, and <b>8</b> were verified by synthesis. Compound <b>3</b> was active against serum deprivation-induced PC12 cell damage and synthetic <b>9</b>–<b>14</b> exhibited activity against Fe²⁺-cysteine induced rat liver microsomal lipid peroxidation.</p></div

Polycycloiridals A–D, Four Iridal-Type Triterpenoids with an α‑Terpineol Moiety from <i>Iris tectorum</i>

Polycycloiridals A–D, four novel iridals with an unprecedented α-terpineol moiety resulting from cyclization of the homofarnesylside chain, were isolated from the ethanol extract of rhizomes of <i>Iris tectorum</i>. Their structures were elucidated on the basis of comprehensive spectroscopic analysis. The absolute configuration of <b>1</b> was determined by the modified Mosher’s method and comparison of experimental and calculated electronic circular dichroism (ECD) spectrum. A possible biosynthetic pathway was postulated