Five New Sesquiterpenoids from Parasenecio petasitoides

From the whole plants of Parasenecio petasitoides, five new sesquiterpenoids were isolated, (E,E)‐3α,9β‐dihydroxy‐6βH,11βH‐13‐norgermacra‐1(10),4‐dien‐11,6‐carbolactone ( 2 ), (E,E)‐2α,9β‐dihydroxy‐6βH,11βH‐13‐norgermacra‐1(10),4‐dien‐11,6‐carbolactone ( 3 ), (E,E)‐2α,9β‐dihydroxy‐6βH,11αH‐13‐norgermacra‐1(10),4‐dien‐11,6‐carbolactone ( 4 ), (E)‐15‐hydroxy‐2‐oxo‐6βH,11αH‐13‐norguaia‐3‐ene‐11,6‐carbolactone ( 7 ), and (E)‐11β,15‐dihydroxy‐2‐oxo‐6βH‐13‐norguaia‐3‐ene‐11,6‐carbolactone ( 8 ), together with three known compounds, deacetyl herbolide A ( 1 ), jacquilenin ( 5 ), and (E)‐15‐hydroxy‐2‐oxo‐6βH,11βH‐13‐norguaia‐3‐ene‐11,6‐carbolactone ( 6 ). The structures of these natural products were elucidated spectroscopically, especially by 1D‐ and 2D‐NMR techniques, in combination with high‐resolution mass spectroscopy.     

Triumfettosterol Id and Triumfettosaponin,a New (Fatty Acyl)‐Substituted Steroid and a Triterpenoid ‘Dimer’ Bis(β‐D‐glucopyranosyl) Ester from the Leaves of Wild Triumfetta cordifolia A. Rich. (Tiliaceae)

Two new triterpenoid derivatives were isolated from the leaves of wild Triumfetta cordifolia A. Rich . and identified to be a (fatty acyl)‐substituted steroid 1 and a triterpenoid saponin ‘dimer’ 2 , named (3β)‐stigmasta‐5,22‐diene‐3,29‐diol 3‐propanoate 29‐triacontanoate and (2α,3β,19α)‐2,3,19‐trimethoxyurs‐12‐ene‐24,28‐dioic acid 24‐[(2α,3β)‐24,28‐bis(β‐D ‐glucopyranosyloxy)‐2‐hydroxy‐24,28‐dioxours‐12‐en‐3‐yl] ester, respectively. These compounds were obtained together with a mixture of known sterols (stigmasterol/β‐sitosterol=(3β,22E)‐stigmasta‐5,22‐dien‐3‐ol/(3β)‐stigmast‐5‐en‐3‐ol) and trans‐tiliroside ( 3 ). The structures 1 and 2 were determined on the basis of NMR data (¹H‐, ¹³C‐, and 2D‐NMR analyses) and mass spectrometry and confirmed by chemical transformations. The antimicrobial activities of trans‐tiliroside ( 3 ) against eight bacterial and two fungal strains were evaluated. This compound showed weak activities on some bacterial strains.     

Photooxygenation of Pregnanes

The course of the singlet‐oxygen reaction with pregn‐17(20)‐enes and pregn‐5,17(20)‐dienes was studied to compare the reactivity of the two alkene moieties present in some steroid families. Thus, from commercially available (3β,5α)‐hydroxy‐androstan‐17‐one and (3β)‐3‐hydroxyandrost‐5‐en‐17‐one, the following 3‐{[(tert‐butyl)dimethylsilyl]oxy}‐substituted, 17(20)‐unsaturated pregnanes were prepared (see Fig. 1): (3β,5α)‐21‐norpregn‐17(20)‐ene 1 ; (3β,5α,17Z)‐pregn‐17(20)‐ene 2 , (3β,5α,16α,17E)‐pregn‐17(20)‐en‐16‐ol 3 , (16β,5α,17E)‐pregn‐17(20)‐en‐16‐ol 4 , (3β,5α,16β,17E)‐pregn‐17(20)‐en‐16‐ol acetate 5 , (3β,16α)‐21‐norpregna‐5,17(20)‐dien‐16‐ol 6 , (3β,16α,17E)‐pregna‐5,17(20)‐dien‐16‐ol 7 , (3β,17Z)‐pregna‐5,17(20)‐diene 8 , (3β,17E)‐pregna‐5,17(20)‐dien‐21‐ol 9 and (3β,17E)‐5,17(20)‐dien‐21‐ol acetate 10 . The oxygenated products (see Fig. 2) obtained from 1 – 10 and ¹O₂, generated by irradiation of Rose Bengal in ³O₂‐saturated pyridine solution, were characterized by ¹H‐, ¹³C‐NMR, and MS (EI, FAB, HR‐EI, ESI‐ and UV‐MALDI‐TOF) data. Major products were those formed by the ene reaction involving as intermediates the corresponding hydroperoxides and the cyclic tautomers of the allylic hydroperoxides, i.e., the corresponding oxiranium oxide‐like intermediate (Scheme 5).     

Terpenoids from Two Dicranopteris Species

Two new compounds, (6S,13S)‐6‐{[β‐D ‐glucopyranosyl‐(1→4)‐α‐L ‐rhamnopyranosyl]oxy}cleroda‐3,14‐dien‐13‐ol ( 1 ) and kadsuric acid 3‐methyl ester ( 2 ), together with nine known compounds, (6S,13E)‐6‐{[β‐D ‐glucopyranosyl‐(1→4)‐α‐L ‐rhamnopyranosyl]oxy}cleroda‐3,13‐dien‐15‐ol ( 3 ), (6S,13S)‐6‐[6‐O‐acetyl‐β‐D ‐glucopyranosyl‐(1→4)‐α‐L ‐rhamnopyranosyl]oxy}‐13‐{[α‐L ‐rhamnopyranosyl‐(1→4)‐β‐D ‐fucopyranosyl]oxy}cleroda‐3,14‐diene ( 4 ), (6S,13S)‐6‐{[6‐O‐β‐D ‐glucopyranosyl‐(1→4)‐α‐L ‐rhamnopyranosyl]oxy}‐13‐{[α‐L ‐rhamnopyranosyl‐(1→4)‐β‐D ‐fucopyranosyl]oxy}cleroda‐3,14‐diene ( 5 ), 15‐hydroxydehydroabietic acid ( 6 ), 15‐hydroxylabd‐8(17)‐en‐19‐oic acid ( 7 ), junicedric acid ( 8 ), (4β)‐kaur‐16‐en‐18‐oic acid ( 9 ), (4β)‐16‐hydroxykauran‐18‐oic acid ( 10 ), and (4β,16β)‐16‐hydroxykauran‐18‐oic acid ( 11 ) were isolated from the fronds of Dicranopteris linearis or D. ampla. Their structures were established by extensive 1D‐ and 2D‐NMR spectroscopy. Compounds 1 and 3 – 8 showed no anti‐HIV activities.     

Sterols from the Stems of Momordica charantia

A new sterol, 5α,6α‐epoxy‐3β‐hydroxy‐(22E,24R)‐ergosta‐8,22‐dien‐7‐one ( 1 ), together with eight known sterols, 5α,6α‐epoxy‐(22E,24R)‐ergosta‐8,22‐diene‐3β,7α‐diol ( 2 ), 5α,6α‐epoxy‐(22E,24R)‐ergosta‐8,22‐diene‐3β,7β‐diol ( 3 ), 5α,6α‐epoxy‐(22E,24R)‐ergosta‐8(14),22‐diene‐3β,7α‐diol ( 4 ), 3β‐hydroxy‐(22E,24R)‐ergosta‐5,8,22‐trien‐7‐one ( 5 ), ergosterol peroxide ( 6 ), clerosterol ( 7 ), decortinol ( 8 ), and decortinone ( 9 ), were isolated from the stems of Momordica charantia. Their structures were elucidated by mean of extensive spectroscopic methods, including ¹H, ¹³C, 2D‐NMR and HR‐EI‐MS, as well as comparison with the literature data. Compounds 1 , 4 , 5 , 8 , and 91 were not cytotoxic against the SK‐Hep 1 cell line.     

Novel Sesquiterpenoids from Siegesbeckia orientalis

Five new sesquiterpenoids, namely, 8β‐(angeloyloxy)‐4β,6α,15‐trihydroxy‐14‐oxoguaia‐9,11(13)‐dien‐12‐oic acid 12,6‐lactone ( 1 ), 4β,6α,15‐trihydroxy‐8β‐(isobutyryloxy)‐14‐oxoguaia‐9,11(13)‐dien‐12‐oic acid 12,6‐lactone ( 2 ), 11,12,13‐trinorguai‐6‐ene‐4β,10β‐diol ( 3 ), (1(10)E,4E,8Z)‐8‐(angeloyloxy)‐6α,15‐dihydroxy‐14‐oxogermacra‐(1(10),4,8,11(13)‐tetraen‐12‐oic acid 12,6‐lactone ( 9 ), and (1(10)E,4β)‐8β‐(angeloyloxy)‐6α,14,15‐trihydroxygermacra‐1(10),11(13)‐dien‐12‐oic acid 12,6‐lactone ( 11 ), and three new artifacts, (1(10)E,4Z)‐8β‐(angeloyloxy)‐9α‐ethoxy‐6α,15‐dihydroxy‐14‐oxogermacra‐1(10),4,11(13)‐trien‐12‐oic acid 12,6‐lactone ( 6 ), (1(10)E,4Z)‐8β‐(angeloyloxy)‐9α,13‐diethoxy‐6α,15‐dihydroxy‐14‐oxogermacra‐1(10),4‐dien‐12‐oic acid 12,6‐lactone ( 7 ), and (1(10)E,4Z)‐8β‐(angeloyloxy)‐9α‐ethoxy‐6α,15‐dihydroxy‐13‐methoxy‐14‐oxogermacra‐1(10),4‐dien‐12‐oic acid 12,6‐lactone ( 8 ), together with the three known sesquiterpenoids 4, 5 , and 10 , were isolated from the aerial parts of Siegesbeckia orientalis L. Their structures were established by spectral methods, especially 1D‐ and 2D‐NMR spectral methods.     

Huangqiyenins G – J,Four New 9,10‐Secocycloartane (=9,19‐Cyclo‐9,10‐secolanostane) Triterpenoidal Saponins from Astragalus membranaceus Bunge Leaves

Four new 9,10‐secocycloartane (=9,19‐cyclo‐9,10‐secolanostane) triterpenoidal saponins, named huangqiyenins G–J ( 1 – 4 , resp.), were isolated from Astragalus membranaceus Bunge leaves. The acid hydrolysis of 1 – 4 with 1M aqueous HCl yielded D ‐glucose, which was identified by GC analysis after treatment with L ‐cysteine methyl ester hydrochloride. The structures of 1 – 4 were established by detailed spectroscopic analysis as (3β,6α,10α,16β,24E)‐3,6‐bis(acetyloxy)‐10,16‐dihydroxy‐12‐oxo‐9,19‐cyclo‐9,10‐secolanosta‐9(11),24‐dien‐26‐yl β‐D ‐glucopyranoside ( 1 ), (3β,6a,10α,24E)‐3,6‐bis(acetyloxy)‐10‐hydroxy‐12,16‐dioxo‐9,19‐cyclo‐9,10‐secolanosta‐9(11),24‐dien‐26‐yl β‐D ‐glucopyranoside ( 2 ), (3β,6α,9α,10α,16β,24E)‐3,6‐bis(acetyloxy)‐9,10,16‐trihydroxy‐9,19‐cyclo‐9,10‐secolanosta‐11,24‐dien‐26‐yl β‐D ‐glucopyranoside ( 3 ), and (3β,6α,10α,24E)‐3,6‐bis(acetyloxy)‐10‐hydroxy‐16‐oxo‐9,19‐cyclo‐9,10‐secolanosta‐9(11),24‐dien‐26‐yl β‐D ‐glucopyranoside ( 4 ).     

A Rare New Cleistanthane Diterpene from the Pericarp of Trewia nudiflora

A minor, unprecedented diterpene, 3β,17‐dihydroxycleistantha‐12,15‐dien‐2‐one ( 1 ), was isolated from the CHCl₃‐soluble part of the EtOH extract of the pericarp of Trewia nudiflora. The structure of 1 was elucidated by means of 1D‐ and 2D‐NMR spectroscopic analyses as well as by HR‐MS. Also isolated were two known triterpenes, glutin‐5‐en‐3‐ol and olean‐18‐en‐3‐one (germanicone), as well as three known sterols, (22E,24R)‐5α,8α‐epidioxyergosta‐6,22‐dien‐3β‐ol, (22E,24R)‐5α,8α‐epidioxyergosta‐6,9(11),22‐trien‐3β‐ol, and (22E,24R)‐6‐methoxyergosta‐7,22‐dien‐3,5‐diol.     

Bruceines K and L from the Ripe Fruits of Brucea javanica

Bruceine K ( 1 ), a pentacyclic C₂₀‐quassinoid bearing a unique 12,20‐epoxy moiety, and bruceine L ( 2 ), along with the ten known compounds (6S,7E)‐6,9,10‐trihydroxy‐ and (6S,7E)‐6,9‐dihydroxymegastigma‐4,7‐dien‐3‐one ( 3 and 4 , resp.), cleomiscosins A–C, luteoline, quercetine, bruceantinol, pinoresinol, and thevetiaflavone, were isolated from the ripe fruits of Brucea javanica. Bruceines K ( 1 ) and L ( 2 ) were determined to be (1β,2α,11β,12β,14ξ,15β)‐12,20‐epoxy‐1,2,11,13,14,15‐hexahydroxypicras‐3‐en‐16‐one and (1β,2α,11β,12β,15β)‐13,20‐epoxy‐1,2,11,12‐tetrahydroxy‐16‐oxo‐15‐(senecioyloxy)picras‐3‐en‐21‐oic acid methyl ester (senecioic acid=3‐methylbut‐2‐enoic acid), respectively, on the basis of NMR (¹H‐ and ¹³C‐NMR, DEPT, ¹H,¹H‐COSY, NOESY, HMQC, and HMBC) and ESI‐MS data. Among the known compounds, (6S,7E)‐6,9,10‐trihydroxy‐ and (6S,7E)‐6,9‐dihydroxymegastigma‐4,7‐dien‐3‐one ( 3 and 4 , resp.), cleomiscosin C, luteoline, quercetine, and thevetiaflavone were isolated for the first time from the Brucea plants.     

Thrombin Inhibitory Constituents from Duranta repens

The C‐alkylated flavonoids 3,7,4′‐trihydroxy‐3′‐(4‐hydroxy‐3‐methylbutyl)‐5,6‐dimethoxyflavone ( 1 ), 3,7‐dihydroxy‐3′‐(4‐hydroxy‐3‐methylbutyl)‐5,6,4′‐trimethoxyflavone ( 2 ) and the trans‐clerodane diterpenoids 6β‐hydroxy‐15,16‐epoxy‐5β,8β,9β,10α‐cleroda‐3,13(16),14‐trien‐18‐oic acid ( 3 ) and 2β‐hydroxy‐15,16‐epoxy‐5β,8β,9β,10α‐cleroda‐3,13(16),14‐trien‐18‐oic acid ( 4 ) were isolated from Duranta repens. Their structures and the relative configuration of 3 and 4 were determined by spectroscopic methods (¹H‐ and ¹³C‐NMR, IR, and MS) and 2D‐NMR experiments. The known flavonoid 5 is also reported for the first time from this species. The compounds 1 , 3 , and 5 showed significant enzyme‐inhibitory activity against thrombin.     

Isolation of a New Carotenoid and Two New Carotenoid Glycosides from Curtobacterium flaccumfaciens pvar poinsettiae

An efficient method for the extraction of the carotenoids from Curtobacterium flaccumfaciens pvar poinsettiae was developed. The glucosides of C.p. 450 (=(all‐E,2R,2′R)‐2‐[4‐(β‐D ‐glucopyranosyloxy)‐3‐methylbut‐2‐enyl]‐2′‐(4‐hydroxy‐3‐methylbut‐2‐enyl)‐β, β‐carotene; 4 ) and of C.p. 473 (=(all‐E,2R,2′S)‐2‐[4‐(β‐D ‐glucopyranosyloxy)‐3‐methylbut‐2‐enyl]‐2′‐(3‐methylbut‐2‐enyl)‐3′,4′‐didehydro‐1′,2′‐dihydro‐β,ψ‐caroten‐1′‐ol; 5 ) were isolated for the first time. In addition, the hitherto unknown 3′,4′‐dihydro derivative of C.p. 450, called C.p. 460 (=(all‐E,2R,2′R)‐2‐(4‐hydroxy‐3‐methylbut‐2‐enyl)‐2′‐(3‐methylbut‐2‐enyl)‐1′,2′‐dihydro‐β,ψ‐caroten‐1′‐ol; 6 ), was identified. The structures were established by UV/VIS, CD, ¹H‐ and ¹³C‐NMR, and mass spectra.     

Two New Tetracyclic Triterpenoids and Other Constituents from Aster Ageratoides var. Oophyllus

Two new tetracyclic triterpenoids shiona‐19(E),21‐dien‐3β‐ol ( 1 ), and shiona‐22(29)‐en‐3β,21‐diol ( 2 ), together with four known compounds shiona‐21‐en‐3β‐ol ( 3 ), friedelinol ( 4 ), β‐sitosterol ( 5 ), and (24R)‐stigmast‐7,22(E)‐dien‐3a‐ol ( 6 ) were isolated from Aster ageratoides var. oophyllus. The structures of two new compounds were established on the basis of IR, MS, ¹H, ¹³C and 2D NMR spectroscopic methods.     

New Triterpenoid Glycosides from Centella asiatica

Four new triterpenoid glycosides named asiaticoside C ( 1 ), D ( 2 ), E ( 3 ), and F ( 4 ) were isolated from the BuOH fraction of the EtOH extract of whole plants of Centella asiatica, together with three known compounds, asiaticoside ( 5 ), madecassoside ( 6 ), and scheffuroside B ( 7 ). Based on FAB‐MS, IR, ¹H‐ and ¹³C‐NMR, and 2D‐NMR data (HMQC, HMBC, COSY), the structures of the new compounds were determined as (2α,3β,4α)‐23‐(acetyloxy)‐2,3‐dihydroxyurs‐12‐en‐28‐oic acid O‐α‐L ‐rhamnopyranosyl‐(1→4)‐O‐β‐D ‐glucopyranosyl‐(1→6)‐β‐D ‐glucopyranosyl ester ( 1 ), (2α,3β)‐2,3‐dihydroxyurs‐12‐en‐28‐oic acid O‐α‐L ‐rhamnopyranosyl‐(1→4)‐O‐β‐D ‐glucopyranosyl‐(1→6)‐β‐D ‐glucopyranosyl ester ( 2 ), asiatic acid 6‐O‐β‐D ‐glycopyranosyl‐β‐D ‐glucopyranosyl ester ( 3 ), (3β,4α)‐3,23‐dihydroxyurs‐12‐en‐28‐oic acid O‐α‐L ‐rhamnopyranosyl‐(1→4)‐O‐β‐D ‐glucopyranosyl‐(1→6)‐β‐D ‐glucopyranosyl ester ( 4 ).     

New Cadinane‐Type Sesquiterpenes from the Roots of Taiwania cryptomerioides Hayata

Six new cadinane‐type sesquiterpenes, (1β,4β,5α,10α)‐1,4‐epoxymuurolan‐5‐ol ( 1 ), (4α,10β)‐4,10‐dihydroxycadin‐1(6)‐en‐5‐one ( 2 ), (2β,3α,4β,6β)‐2,3‐dihydroxycadin‐1(10)‐en‐5‐one ( 3 ), (2β,3α)‐α‐corocalene‐2,3‐diol ( 4 ), (7S)‐α‐calacoren‐14‐ol ( 5 ), and (8β,9β,10β)‐8,9‐epoxycalamenene‐3,10‐diol ( 6 ) together with one known compound, (8β,9β,10β)‐8,9‐epoxycalamenen‐10‐ol ( 7 ), were isolated from the roots of Taiwania cryptomerioides. The structures of the new constituents were essentially elucidated by spectral evidence.     

New Triterpenoid and Ergostane Glycosides from the Leaves of Hydrocotyle umbellata L.

Two new triterpenoid glycosides, together with two new ergostane glycosides, umbellatosides A–D ( 1 – 4 , resp.), have been isolated from the leaves of Hydrocotyle umbellata L. Their structures were established by 2D‐NMR spectroscopic techniques (¹H,¹H‐COSY, TOCSY, NOESY, HSQC, and HMBC) and mass spectrometry as 3β,22β‐dihydroxy‐3‐O‐[α‐L ‐rhamnopyranosyl‐(1→2)‐β‐D ‐glucuronopyranosyl]olean‐12‐en‐28‐oic acid 28‐O‐β‐D ‐glucopyranosyl ester ( 1 ), 3‐O‐[α‐L ‐rhamnopyranosyl‐(1→2)‐β‐D ‐glucuronopyranosyl]oleanolic acid 28‐O‐β‐D ‐glucopyranosyl ester ( 2 ), (3β,11α,26)‐ergosta‐5,24(28)‐diene‐3,11,26‐triol 3‐O‐(β‐D ‐glucopyranosyl)‐11‐O‐(α‐L ‐rhamnopyranosyl)‐26‐O‐β‐D ‐glucopyranoside ( 3 ), and (3β,11α,21,26)‐ergosta‐5,24(28)‐diene‐3,11,21,26‐tetrol 3‐O‐(β‐D ‐glucopyranosyl)‐11‐O‐(α‐L ‐rhamnopyranosyl)‐26‐O‐β‐D ‐glucopyranoside ( 4 ).     

New Acylated Triterpene Saponins from Polygala arenaria

Eight new acylated triterpene saponins 1 – 8 were isolated from the roots of Polygala arenaria as four inseparable (E)/(Z) mixtures of the 4‐methoxycinnamoyl and 3,4‐dimethoxycinnamoyl derivatives by repeated MPLC over silica gel. Their structures were established mainly by 600‐MHz 2D‐NMR techniques (¹H,¹H‐COSY, TOCSY, NOESY, HSQC, HMBC) as 3‐O‐(β‐D ‐glucopyranosyl)presenegenin 28‐(O‐β‐D ‐galactopyranosyl‐(1→4)‐O‐[β‐D ‐glucopyranosyl‐(1→3)]‐O‐β‐D ‐xylopyranosyl‐(1→4)‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐{4‐O‐[(E)‐4‐methoxycinnamoyl]}‐β‐D ‐fucopyranosyl) ester and its (Z)‐isomer ( 1 / 2 ), 3‐O‐(β‐D ‐glucopyranosyl)presenegenin 28‐(O‐β‐D ‐galactopyranosyl‐(1→4)‐O‐[β‐D ‐glucopyranosyl‐(1→3)]‐O‐β‐D ‐xylopyranosyl‐(1→4)‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐{4‐O‐[(E)‐3,4‐dimethoxycinnamoyl]}‐β‐D ‐fucopyranosyl) ester and its (Z)‐isomer ( 3 / 4 ), 3‐O‐(β‐D ‐glucopyranosyl)presenegenin 28‐(O‐β‐D ‐glucopyranosyl‐(1→3)‐O‐α‐L ‐arabinopyranosyl‐(1→4)‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐{4‐O‐[(E)‐4‐methoxycinnamoyl]}‐β‐D ‐fucopyranosyl) ester and its (Z)‐isomer ( 5 / 6 ), and 3‐O‐(β‐D ‐glucopyranosyl)presenegenin 28‐(O‐β‐D ‐glucopyranosyl‐(1→3)‐O‐α‐L ‐arabinopyranosyl‐(1→4)‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐{4‐O‐[(E)‐3,4‐dimethoxycinnamoyl]}‐β‐D ‐fucopyranosyl) ester and its (Z)‐isomer ( 7 / 8 ) (presenegenin=(2β,3β)‐2,3,27‐trihydroxyolean‐12‐ene‐23,28‐dioic acid). In our in vitro lymphocyte proliferation assay (Jurkat T‐leukemia cells), a fraction containing 1 – 4 showed a concentration‐dependent immunomodulatory effect. This effect was not found for the prosapogenin (tenuifolin=3‐O‐(β‐D ‐glucopyranosyl)presenegenin), underlining the importance of the acyl? oligosaccharidic moiety.     

Hydrolytic Reaction of Plant Extracts to Generate Molecular Diversity: New Dammarane Glycosides from the Mild Acid Hydrolysate of Root Saponins of Panax notoginseng

Molecular diversity was generated by hydrolyzing the crude root saponins of Panax notoginseng (Burk .) F. H. Chen under mild acidic condition (AcOH/EtOH 1 : 1). From the acid hydrolysate, five new dammarane glycosides, named notoginsenoside T₁ (=(3β,6α,12β,20E,23RS)‐24,25‐epoxy‐6‐[(β‐D ‐glucopyranosyl)oxy]‐dammar‐20(22)‐ene‐3,12,23‐triol; 1 ), notoginsenoside T₂ (=(3β,6α,12β,20E,23RS)‐24,25‐epoxy‐6‐[(β‐D ‐glucopyranosyl)oxy]‐23‐methoxydammar‐20(22)‐ene‐3,12‐diol; 2 ), notoginsenoside T₃ (=(3β,6α,12β,20S)‐6‐[(β‐D ‐glucopyranosyl)oxy]‐20‐ethoxydammar‐24‐ene‐3,12‐diol; 3 ), notoginsenoside T₄ (=(3β,6α,12β,20S,22E,24RS)‐6‐[(β‐D ‐glucopyranosyl)oxy]dammar‐22‐ene‐3,12,20,24,25‐pentol; 4 ), and notoginsenoside T₅ (=(3β,6α,12β, 24E)‐6‐[(β‐D ‐xylopyranosyl‐(1→2)‐β‐D ‐glucopyranosyl)oxy]dammara‐20(21),24‐diene‐3,12‐diol; 5 ), were isolated, together with 15 known dammarane glycosides, and their structures were elucidated on the basis of spectroscopic evidence. Among the known compounds, ginsenosides Rg₃ and Rh₁ were isolated as major constituents, in addition to ginsenosides Rg₅, Rh₄, and a mixture of (20R)‐ and (20S)‐25‐hydroxyginsenoside Rh₁, all of which were obtained from P. notoginseng for the first time.     

Lignans from the Bark of Magnolia kobus

The Et₂O‐soluble fraction from the bark of Magnolia kobus led to the isolation of two new lignans, (+)‐(7α,7′α,8α,8′α)‐3′,4,4′,5,5′‐pentamethoxy‐7,9′: 7′,9‐diepoxylignan‐3‐ol ( 1 ) and (+)‐(7α,7′α,8α,8′α)‐4,5‐dimethoxy‐3′,4′‐(methylenedioxy)‐7,9′: 7′,9‐diepoxylignan‐3‐ol ( 2 ), along with five known lignans 3 – 7 . Their structures were established on the basis of various spectroscopic analyses including 1D‐ (¹H, ¹³C, and DEPT) and 2D‐NMR (COSY, NOESY, HMQC, and HMBC) and by comparison of their spectral data with those of related compounds.     

New Steryl Esters of Fatty Acids from the Mangrove Fungus Aspergillus awamori

The polyhydroxylated ergostane‐type sterol 9 , its derivatives 10 – 15 , and the fatty acid esters 1 – 8 were isolated from a fungus strain which was collected from mangrove areas at Wenchang, Hainan Province, P. R. China, exhibited potent cytotoxic activity, and was identified as Aspergillus awamori. The structures of 1 – 15 were elucidated by spectroscopic and chemical methods. Among them, the six steryl esters 1 – 6 of fatty acids were new compounds, i.e., (3β,5α,6α,22E)‐ergosta‐7,22‐diene‐3,5,6‐triol 6‐palmitate ( 1 ), (3β,5α,6α,22E)‐ergosta‐7,22‐diene‐3,5,6‐triol 6‐stearate ( 2 ), (3β,5α,6α,22E)‐ergosta‐7,22‐diene‐3,5,6‐triol 6‐oleate ( 3 ), (3β,5α,6α,22E)‐ergosta‐7,22‐diene‐3,5,6‐triol 6‐linoleate ( 4 ), (3β,5α,6β,22E)‐ergosta‐7,22‐diene‐3,5,6‐triol 6‐palmitate ( 5 ), and (3β,5α,6β,22E)‐ergosta‐7,22‐diene‐3,5,6‐triol 6‐stearate ( 6 ). The related known fatty acids stearic acid (=octadecanoic acid) and palmitic acid (=octadecanoic acid) were also obtained. A speculative biogenetic relationship of the metabolites is proposed. The known polyhydroxylated sterols and derivatives showed cytotoxic activities, in agreement with earlier reports. The cytotoxic activities against B16 and SMMC‐7721 cell lines of the new steryl esters 1 – 6 by the MTT method were weak.     

Constituents from the Roots of Semiaquilegia adoxoides

In present literature search, some cyano-containing compounds, which are very rare in plants, from the traditional anticancer herb Tiankuizi were reported. To find more cyano-containing compounds in the important plant Semiaquilegia adoxoides （DC） Makino （Chinese name Tiankuizi）, the isolation of the chemical constituents was investigated for advancing the research. Two new compounds, a new alkaloid, 1,2,3,4-tetrahydro-6-hydroxy-1[（3,4-dihydroxyphenyl）methyl]-7-methoxy-2,2-dimethyl-isoquinolinium, named Semiaquilegine A （1）, and a new ester, 3-（4＇-hydroxyphenyl）-2-propenoic acid （4＂-carboxyl）-phenyl ester （2）, and four cyano-containing compounds, （Z）-6a-（β-D-glucosyloxy）-4a,5a-dihydroxy-2-cyclohexene-△^1,a-acetonitrile （3）, （L0-6α-（β-D-glucosyloxy）-4α-hydroxy-2-cyclohexene-△^1,α-acetonitrile （4）, lithospermoside （5）, ehretioside B （6）, as well as eleven known compounds, were isolated from the roots of Semiaquilegia adoxoides. The structures of new compounds 1 and 2 were elucidated mainly by 1D/2D-NMR techniques. Very unusual cyano-containing compounds 3 and 4 were first isolated from Ranunculaceae family. Hitherto, there were six cyano-containing compounds found in the herb.