Chromenone Glucosides Acylated with Monoterpene Acids from the Leaves of Eucalyptus camaldulensis var. obtusa

Three new chromenone glucosides acylated with monoterpene acids, eucamaldusides A ( 1 ), B ( 2 ), and C ( 3 ), were isolated from the leaves of Eucalyptus camaldulensis var. obtusa, together with the five known compounds ursolic acid lactone, obtusilin, β‐sitosterol glucoside, 4‐hydroxybenzoic acid, and cypellocarpin C. The structures of the new compounds were established by exhaustive 1D‐ and 2D‐NMR spectroscopic studies. Their configuration was determined by measuring the [α]_D of the known methyl esters of the monoterpene acids obtained by methanolysis of 1 – 3 .     

Phenylpropanoid Esters of Rhamnose from Buddleja asiatica

Four new phenylpropanoid esters of rhamnose, asiatisides A–D, along with the known compounds, buergeriside C₁ ( 5 ), p‐methoxycinnamic acid, ferulic acid, and O‐methylferulic acid were obtained from the aerial parts of Buddleja asiatica Lour by chromatographic methods. The new compounds were elucidated as 3‐O‐acetyl‐4‐O‐(p‐methoxycinnamoyl)‐α‐L ‐rhamnopyranose ( 1 ), 3‐O‐acetyl‐4‐O‐feruloyl‐α‐L ‐rhamnopyranose ( 2 ), 2‐O‐acetyl‐4‐O‐(O‐methylferuloyl)‐α‐L ‐rhamnopyranose ( 3 ), 2‐O‐acetyl‐4‐O‐(p‐methoxycinnamoyl)‐α‐L ‐rhamnopyranose ( 4 ) by spectral data (1D‐, 2D‐NMR, and MS), respectively.     

Tasumatrols P – T,Five New Taxoids from Taxus sumatrana

The phytochemical investigation of the more polar fractions from the leaves and twigs of Taxus sumatrana (Taxaceae) afforded five new taxane diterpene esters, tasumatrols P–T ( 1 – 5 ) possessing an 11(15→1),11(10→9)‐diabeotaxane skeleton. Compounds 1, 4 , and 5 contain an α‐hydroxy group at C(14), while 3 has no OH group at either C(13) or C(14). Compound 2 is a natural 4,5‐acetonide derivative, while 4 has an unusual spiro‐connected 2‐hydroxy‐2‐phenyl‐1,3‐dioxolane ring. Ten known taxoids, were also isolated in the course of the chromatographic fractionation. Five additional new O‐acetyl derivatives 3a, 4a, 4b, 5a , and 5b were prepared from the taxanes 3 – 5 . The structures of all new compounds were established on the basis of their spectroscopic analyses. Compound 1 showed mild cytotoxic activity against human Hela and Daoy tumor cells.     

Sesquiterpene Lactones from Daucus glaber

Six new sesquiterpene lactone esters, daucoguaianolactones A–F ( 1 – 6 ), and one new sesquiterpene lactone, daucoeudesmanolactone A ( 7 ) were isolated from the leaves and stems of Daucus glaber (Forssk .) Thell ., along with the known sesquiterpene lactones talasins A and B and badkhysin. The structures of 1 – 6 were established on the basis of extensive 1D‐ and 2D‐NMR spectroscopic studies and that of 7 by X‐ray crystallography. Compounds 4, 7 , and talasins A and B showed moderate cytotoxicity against P‐388 leukemia cells.     

Trichodermates A–F,New Cytotoxic Trichothecenes from the Plant Pathogenic Fungus Trichoderma sp.

Trichodermates A – F ( 1 – 6 , resp.), six new trichothecene polyunsaturated octadioic acid esters, and (?)‐harzianum B ( 7 ) were isolated from the fermentation extract of Trichoderma sp., a plant pathogenic fungus isolated from stem rot of an unidentified tree in Thailand. The structures of 1 – 7 were elucidated by NMR experiments. The absolute configuration at C(12) in 3 was assigned by in situ dimolybdenum circular dichroism method, whereas that in 7 was deduced after hydrolysis of 7 to 8 via modified Mosher's method. Compounds 1 and 2 showed modest cytotoxic activities against the K562 (human myelogenous leukemia) cell line with IC₅₀ values of 12.12 and 13.08 μM , respectively.     

Three New Glycosides from the Stems of Miliusa balansae

Three new glycosides with the same saccharides, namely miliusoside A ( 1 ), miliusoside B ( 2 ), and miliusoside C ( 3 ), together with five known compounds were isolated from the stems of Miliusa balansae. Their structures were elucidated on the basis of detailed spectroscopic analysis and by comparison with the spectra of related model compounds. There was a rarely encountered α‐D ‐apiose moiety occurring in all new compounds.     

Three New Phthalides from Gnaphalium adnatum

Three new phthalides, gnaphalides A–C ( 1 – 3 , resp.), together with three known phthalides, were isolated from the aerial part of Gnaphalium adnatum. The structures of the new compounds were elucidated as 6‐(1,1‐dimethylprop‐2‐en‐1‐yl)‐5,7‐dihydroxy‐2‐benzofuran‐1(3H)‐one ( 1 ), 5‐hydroxy‐7‐[(2‐hydroxy‐3‐methylbut‐3‐en‐1‐yl)oxy]‐2‐benzofuran‐1(3H)‐one ( 2 ), and 1,3‐dihydro‐7‐[(3‐methylbut‐2‐en‐1‐yl)oxy]‐1‐oxo‐2‐benzofuran‐5‐yl β‐D ‐glucopyranoside ( 3 ) on the basis of spectral analyses. The structure of 1 was also confirmed by X‐ray crystallographic analysis. The three known phthalides, identified as 5,7‐dihydroxyisobenzofuran‐1(3H)‐one ( 4 ), anaphatol ( 5 ), and 7‐O‐(β‐glucopyranosyl)‐5‐hydroxyisobenzofuran‐1(3H)‐one ( 6 ), were isolated from the genus Gnaphalium for the first time.     

Dapholidins A – C,New Isomeric Biisoflavonoids From Daphne oleoides

Three new isomeric biisoflavonoids, dapholidins A–C ( 1 – 3 , resp.), have been isolated from the AcOEt‐soluble fraction of the MeOH‐soluble extract of the roots of Daphne oleoides, along with the known compounds daphwazirin ( 4 ), daphnetin 8‐O‐β‐D ‐glucopyranoside ( 5 ), daphnin ( 6 ), daphneticin 4″‐O‐β‐D ‐glucopyranoside ( 7 ), and 6,7‐dihydroxy‐3‐methoxy‐8‐[2‐oxo‐2H‐1‐benzopyran‐7‐(O‐β‐D ‐glucopyranosyl)‐8‐yl]‐2H‐1‐benzopyran‐2‐one ( 8 ). The structures of the new compounds were determined by spectroscopic analyses, including 1D‐ and 2D‐NMR.     

Eight New Cucurbitane Glycosides,Kuguaglycosides A – H,from the Root of Momordica charantia L.

Eight new cucurbitane glycosides, kuguaglycosides A–H ( 1 – 8 , resp.), together with five known analogues, 3β,23‐dihydroxycucurbita‐5,24‐dien‐7β‐yl β‐D ‐glucopyranoside ( 9 ), karaviloside III ( 10 ), karaviloside V ( 11 ), karaviloside XI ( 12 ), and momordicoside K ( 13 ), were isolated from the root of Momordica charantia L. The structures of the new compounds were determined on the basis of spectroscopic and chemical methods.     

Five New Tetranortriterpenoids from the Seeds of Toona ciliata

Five new tetranortriterpenoids, toonaciliatones B–F ( 1 – 5 , resp.), together with four known compounds, dihydrocedrelone ( 6 ), cedrelone ( 7 ), 6α‐acetoxyazadirone ( 8 ), and 6α‐acetoxy‐14β,15β‐epoxyazadirone ( 9 ), were isolated from the seeds of Toona ciliata. Their structures were elucidated by spectroscopic methods, including 1D‐ and 2D‐NMR spectroscopy.     

New Alkaloids from Aconitum vaginatum

Two new amide alkaloids, vaginatunine A and B ( 1 and 2 , resp.), and a new C₁₈‐diterpenoid alkaloid vaginatunine C ( 3 ), together with four known alkaloids, were isolated from the tubers of Aconitum vaginatum. Their structures were determined by means of spectroscopic analyses and comparison of the data with those reported previously.     

Five New Aromatic Glycosides from Carthamus tinctorius

Five new aromatic glycosides, 1 – 5 , named as carthamosides B₄–B₈, together with three known compounds, 4′‐(hydroxyphenacyl)‐β‐D ‐glucopyranoside ( 6 ), benzyl‐O‐α‐L ‐rhamnopyranosyl‐(1→6)‐β‐D ‐glucopyranoside ( 7 ), and 4‐(methoxybenzyl)‐O‐β‐D ‐glucopyranoside ( 8 ), have been isolated from the air‐dried flower of Carthamus tinctorius. Their structures were identified on the basis of chemical and spectroscopic methods.     

Baimantuoluolines D – F,Three New Withanolides from the Flower of Datura metel L.

Three new withanolide compounds, named baimantuoluolines D–F, along with three known withanolides and a lignan were isolated from the flower of Datura metel L., the parts effective against psoriasis. The structures of the new compounds were elucidated as (5α,6β,12β,20R,22R,24R,25S)‐21,24‐epoxy‐5,6,12‐trihydroxy‐27‐methoxy‐1‐oxowith‐2‐enolide ( 1 ), (5α,6β,12β,20R,22R,24R,25S)‐21,24‐epoxy‐5,6,12,27‐tetrahydroxy‐1‐oxowith‐2‐enolide ( 2 ), and (5α,6β,12β,22R)‐5,6,12,21‐tetrahydroxy‐1‐oxowith‐24‐enolide( 3 ) on the basis of physicochemical evidence.     

Five New Xanthenone O‐Glycosides from the Roots of Polygala sibirica L.

Five new xanthenone O‐glycosides, sibiricaxanthone C ( 1 ), sibiricaxanthone D ( 2 ), sibiricaxanthone E ( 3 ), sibiricaxanthone F ( 4 ), and sibiricaxanthone G ( 5 ) were isolated from the roots of Polygala sibirica L., together with the six known xanthenone glycosides 6 – 11 . The structures of new compounds were elucidated on the basis of spectral data and acid hydrolysis.     

Three New Triterpene Saponins from Hemsleya chinensis

Three new triterpenoid saponins, xuedanglycosides A–C ( 1 – 3 , resp.), along with six known ones, were isolated from the rhizomes of Hemsleya chinensis. By detailed analysis of the NMR spectra, by chemical methods, and by comparison with spectral data of known compounds, the structures of new compounds were determined to be 16α,23α‐epoxy‐2β,3α,20β‐trihydroxy‐10α,23α‐cucurbita‐5,24‐dien‐11‐on‐2‐yl β‐D ‐glucopyranoside ( 1 ), 2β,3α,16α,20β‐tetrahydroxycucurbita‐5,25‐diene‐11,22‐dion‐2‐yl β‐D ‐glucopyranoside ( 2 ), and oleanolic acid 28‐O‐β‐xylopyranosyl‐(1→6)‐O‐β‐glucopyranoside ( 3 ). In addition, hemslecin A 2‐O‐β‐D ‐glucopyranoside ( 6 ), hemsamabilinin B ( 7 ), and hemslonin A ( 9 ) were obtained for the first time from this plant.     

Heteroclitins N – Q,New Compounds from Stems of Kadsura heteroclita (Roxb.) Craib

From the stems of Kadsura heteroclita (Roxb .) Craib , a new novel C₁₉ homolignan, heteroclitin N ( 1 ), as well as three new lignans, heteroclitins O? Q ( 2 – 4 ), were isolated. Their structures were elucidated based on spectral analysis, including 1D and 2D NMR experiments. There is an additional spirocyclic oxirane system in heteroclitin O ( 2 ), which is the first example of a lignan with an oxirane ring in a spirobenzofuranoid dibenzocyclooctene structure in the genus Kadsura.     

Nine New Sesquiterpenes from Dendrobium nobile

Nine new sesquiterpenes, i.e., dendronobilins A–I ( 1 – 9 ), with copacamphane‐type ( 1 ), picrotoxane‐type ( 2 – 6 ), muurolene‐type ( 7 ), alloaromadendrane‐type ( 8 ), and cyclocopacamphane‐type ( 9 ) skeletons, were isolated from the 60% EtOH extract of the stems of Dendrobium nobile. Their structures were established as (1R,2R,4S,5S,6S,8S,9R)‐2,8‐dihydroxycopacamphan‐15‐one ( 1 ), (2β,3β,4β,5β)‐2,4,11‐trihydroxypicrotoxano‐3(15)‐lactone ( 2 ), (2β,3β,5β,9α,11β)‐2,11‐epoxy‐9,11,13‐trihydroxypicrotoxano‐3(15)‐lactone ( 3 ), (2β,3β,5β,12R*)‐2,11,13‐trihydroxypicrotoxano‐3(15)‐lactone ( 4 ), (2β,3β,5β,12S*)‐2,11,13‐trihydroxypicrotoxano‐3(15)‐lactone ( 5 ), (2β,3β,5β,9α)‐9,10‐cyclo‐2,11,13‐trihydroxypicrotoxano‐3(15)‐lactone ( 6 ), (9β,10α)‐muurol‐4‐ene‐9,10,11‐triol ( 7 ), (10α)‐alloaromadendrane‐10,12,14‐triol ( 8 ), and (5β)‐cyclocopacamphane‐5,12,15‐triol ( 9 ) on the basis of spectroscopic analysis. The absolute configuration of compound 1 was tentatively assigned as (1R,2R,4S,5S,6S,8S,9R) according to its CD spectrum and the octant rule. Compounds 1 and 4 – 9 were inactive in our preliminary in vitro immunomodulatory bioassay.     

Further Alkaloids from the Fruits of Daphniphyllum longeracemosum

Three new Daphniphyllum alkaloids, daphlongeranines C–E ( 1 – 3 ), along with 13 known ones, were isolated from the fruits of Daphniphyllum longeracemosum. Their structures were elucidated on the basis of extensive spectroscopic analyses, especially 2D‐NMR experiments.     

Phenolic Glycosides from the Chinese Liverwort Reboulia hemisphaerica

Four new phenolic glycosides, named rebouosides A–D ( 1 – 4 , resp.), along with three known ones 2‐(3,4‐dihydroxyphenyl)ethyl 2‐O‐α‐L ‐rhamnopyranosyl‐β‐D ‐allopyranoside ( 5 ), 2‐(3,4‐dihydroxyphenyl)ethyl β‐D ‐allopyranoside ( 6 ), 2‐(3,4‐dihydroxyphenyl)ethyl β‐D ‐glucopyranoside ( 7 ), and a nucleoside, inosine ( 8 ), were isolated from Chinese liverwort Reboulia hemisphaerica. Their structures were elucidated by acidic hydrolysis and extensive spectroscopic methods, including 2D‐NMR techniques.     

New Diterpene Alkaloids from Aconitum sungpanense var. leucanthum

Five new C₁₉ diterpene alkaloids, leucanthumsines A ( 1 ), B ( 2 ), C ( 3 ), D ( 4 ), and E ( 5 ), were isolated from the Chinese medicinal herb Aconitum sungpanense var. leucanthum, together with the known C₁₉ diterpene alkaloids pseudaconine, neoline, 1‐O‐methyldelphisine, crassicaudine, chasmanine, talatisamine, indaconitine, ezochansmanine, and leueantine D. The structures of these new alkaloids were elucidated by HR‐MS and advanced NMR methods, including ¹H‐ and ¹³C‐NMR (DEPT), ¹H,¹H‐COSY, HMQC, and HMBC experiments.