A new natural nucleotide and other antibacterial metabolites from an endophytic Nocardia sp.

Nine compounds were isolated from Nocardia sp. YIM 64630, and their structures were elucidated as 5′-O-acetyl-2′-deoxyuridine (1), 22E,24R-5α,6α-epoxyergosta-8(14),22-diene-3β,7α-diol (2), 22E,24R-5α,6α-epoxyergosta-8,22-diene-3β,7α-diol (3), 22E,24R-ergosta-7,22-diene-3β,5α,6β-triol (4), 5α,8α-epidioxyergosta-6,22-dien-3β-ol (5), 4′,5,6-trihydroxy-7-methoxyisoflavone (6), 2,4,4′-trihydroxy-deoxybenzoin (7), methyl [4-hydroxyphenyl]acetate (8) and daidzein by extensive spectroscopic analyses. Compound 1 was isolated from natural resources for the first time. The antimicrobial and antioxidant activities of compounds 1–8 were investigated.     

Constituents of Fruit Bodies of Tramete orientalis

A known sterol, 5α,6α-epoxy-5α-crgosta-8(14),22E-diene-3β,7α-diol ( 1 ), and two new sterols, 5α,6α-epoxy-3β,8β,14α-trihydroxy-5α-ergost-22E-en-7-one ( 2 ), (3α,5α),(8β,11β)-diepidioxy-ergost-22E-en-12-one ( 3 ), were isolated and characterized from dried fruit bodies of Trametes orientalis. Their structures were elucidated according to spectral methods.     

Additional Minor Phytoecdysteroids of Serratula wolffii

Three new and one known ecdysteroids were identified in the MeOH extract of the roots of Serratula wolffii. The new compounds isolated were (11α)‐11‐hydroxyshidasterone ( 1 ), (2β,3α,5β,14β,22R)‐2,3,20,22,25‐pentahydroxycholest‐7‐en‐6‐one ( 2 ), and (2β,3α,5β,22R)‐2,3,20,22,25‐pentahydroxycholest‐7‐en‐6‐one ( 3 ), together with the known ponasterone A ( 4 ). This latter compound was now better characterized than earlier. The structures of compounds 1 – 4 were established by extensive spectroscopic techniques, including one‐ and two‐dimensional NMR methods.     

New Sterol Derivatives from the Marine Sponge Xestospongia sp.

Chemical examination of a marine sponge Xestospongia sp. resulted in the isolation of 20 sterol derivatives ( 1 – 20 ), including eight new sterols namely aragusterols J – L ( 1 – 3 ), (5α,7α,12β,22E)‐7,12,18‐trihydroxystigmast‐22‐en‐3‐one ( 4 ), (5α,7α,12β,24R)‐ and (5α,7α,12β,24S)‐7,12,20‐trihydroxystigmastan‐3‐one ( 5 / 6 ), and (5α,7α,12β,22E,24R)‐ and (5α,7α,12β,22E,24S)‐7,12,20‐trihydroxyergost‐22‐en‐3‐one ( 7 / 8 ). The structures of new compounds were determined through extensive spectroscopic analyses and chemical conversion. The sterol diversity was mainly characterized by the presence of a cyclopropane unit at side chain, while compound 4 with 18‐hydroxymethyl group was found in stigmasterol family for the first time. Cytotoxic test revealed the inhibitory effects of compounds 1 , 4 , and 17 against human leukemia cell line K562 with IC₅₀ values of 18.3, 24.1, and 34.3 μm , respectively.     

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.     

New Cycloartane and Flavonol Glycosides from Corchorus depressus

Two new monodesmosidic cycloartane triterpene glycosides, depressosides E and F, and two new flavonol glycosides, depressonol A and B, were isolated from the butanol‐soluble part of the EtOH extract of Corchorus depressus L . The structures of the new compounds were elucidated as (22R,24S)‐22,25‐epoxy‐9,19‐cyclolanostane‐3β,16β,24‐triol 3‐[α‐L ‐rhamnopyranosyl‐(1→4)‐β‐D ‐glucopyranoside] ( 1 ), (22R,24S)‐22,25‐epoxy‐9,19‐cyclolanostane‐3β,16β,24‐triol 3‐[α‐D ‐glucopyranosyl‐(1→3)‐β‐D ‐glucopyranoside] ( 2 ), kaempferol 3‐[β‐D ‐glucopyranosyl‐(1→4)‐β‐D ‐galactopyranoside] 7‐[α‐L ‐arabinofuranoside] ( 4 ), and kaempferol 3‐[β‐D ‐glucopyranosyl‐(1→6)‐β‐D ‐galactopyranoside] 7‐[α‐L ‐arabinofuranoside] ( 5 ) on the basis of chemical evidence and detailed spectroscopic studies.     

Studies on the Constituents of Ganoderma Lucidum

The methanolic extract of fruit bodies of cultivated Ganoderma lucidum was separated by silica gel column chromatography and preparative thin-layer chromatography to give ten compounds. On the basis of spectral analysis, chemical procedures and gas chromatography, d-mannitol (1), ergosta-7, 22-dien-3β-yl palmitate (2), ergosterol (3), ergosta-7, 22-dien-3β-ol (4), 5α-lanosta-7,9(11),24-trien-3β,26-diol (5), ergosterol peroxide (6), 24,25,26-trihydroxy-5α-lanosta-7,9(11)-dien-3-one (7), 5α-lanosta-7,9(11)-dien-3β,24,25,26-tetraol (8) and 8,9-epoxyergosta-5,22-dien-3β,15-diol (9) were identified. Among these compounds, 8,9-epoxyergosta-5,22-dien-3β,15-diol was first separated from Ganoderma lucidum.     

Withanolides from Physalis alkekengi var. francheti

Two new withanolides, namely (20S,22R)‐15α‐acetoxy‐5α‐chloro‐6β,14β‐dihydroxy‐1‐oxowitha‐2,24‐dienolide ( 1 ) and (22R)‐5β,6β : 14α,17 : 14β,26‐triepoxy‐2α‐ethoxy‐13,20,22‐trihydroxy‐1,15‐dioxo‐16α,24‐cyclo‐13,14‐secoergosta‐18,27‐dioic acid 18→20,27→22‐dilactone ( 2 ), along with six known compounds, physagulin B ( 3 ), withangulatin A ( 4 ), physalin I ( 5 ), withaminimin ( 6 ), physagulin J ( 7 ), and ergosta‐5,25‐diene‐3β,24ξ‐diol ( 8 ), were isolated from the whole plant of Physalis alkekengi var. francheti. Their structures were elucidated on the basis of spectroscopic analyses.     

Cyclopeptide and Terpenoids from Tripterygium wilfordii Hook. f.

The EtOH extract of dried root bark of Tripterygium wilfordii Hook. f. (Celastraceae) afforded a novel macrolactone cyclopeptide named triptotin L (=cyclo[L ‐alanyl‐L ‐alanyl‐3‐(4,4,9‐trimethyldecyl‐3‐hydroxypropanoylglycyl‐L ‐valyl‐L ‐leucyl; 1 ), the new triterpene 2β,6α,22β‐trihydroxy‐24,29‐dinor‐D:A‐friedoolean‐4‐ene‐3,21‐dione named 6α‐hydroxytriptocalline A (=(2β,6α,8α,9β,10α,13α,14β,20β,22β)‐2,6,22‐trihydroxy‐9,13‐dimethyl‐24,25,26,30‐tetranorolean‐4‐ene‐3,21‐dione; 2 ), the new diterpenoid 11,16‐dihydroxy‐14‐methoxy‐18(4→3) abeo‐abieta‐3,8,11,13‐tetraene‐18‐oic acid named 16‐hydroxytriptobenzene H (=(4aS,10aS)‐3,4,4a,9,10,10a‐hexahydro‐5‐hydroxy‐7‐(2‐hydroxy‐1‐methylethyl)‐8‐methoxy‐1,4a‐dimethylphenanthrene‐2‐carboxylic acid; 3 ), and the abietane diterpenoid alkaloid named triptotin J (=(7aS,11aS,11bS)‐7,7a,8,9,10,11,11a,11b‐octahydro‐11b‐hydroxy‐α,α,8,8,11a‐pentamethyl‐6H‐naphth[1,2‐d]azepine‐4‐methanol; 4 ). Their structures were established on the basis of spectroscopic studies.     

Withanolide Compounds from the Flower of Datura metel L.

Three new withanolide compounds named baimantuoluoline A ( 1 ), B ( 2 ), and C ( 3 ) and the two known withanolides withafastuosin E ( 4 ) and withametelin C ( 5 ) were isolated from the fraction exhibiting activity for psoriasis in the flower of Datura metel L. The three new structures were determined as (5α,6α,7α,12β,15β,22R)‐6,7‐epoxy‐5,12,15‐trihydroxy‐1‐oxowitha‐2,24‐dienolide ( 1 ), (5α,6β,15β,22R)‐ 5,6,15,21‐tetrahydroxy‐1‐oxowith‐24‐enolide ( 2 ), and (5α,6β,12β,22R)‐5,6,12,21‐tetrahydroxy‐27‐methoxy‐1‐oxowitha‐2,24‐dienolide ( 3 ) on the basis of extensive spectroscopic data (HR‐ESI‐MS, ¹H‐ and ¹³C‐NMR, ¹H,¹H‐COSY, HSQC, HMBC, and NOESY) (withanolide=22‐hydroxyergostan‐26‐oic acid δ‐lactone).     

Sesquiterpenoids from Chloranthus spicatus （Thunb.） Makino

Two new sesquiterpenoids, namely 1β,4β-dihydroxy-5 α,8β（H）-eudesm-7（11）Z-en-8,12-olide （1） and 1β,4α-dihydroxy-5α,8β（H）-eudesm-7（11）Z-en-8,12-olide （2）, along with six known ones, homalomenol A （3）, oplodiol （4）, 5α,7α（H）-6,8-cycloeudesma-1β,4β-diol （5）, oplopanone （6）, 4β,10α-dihydroxyaromadendrane （7） and spathulenol （8）, were isolated from the aerial part of Chloranthus spicatus （Thunb.） Makino, and their structures were established by spectroscopic methods.     

Diversity of Sesquiterpenoids from Carpesium cernuum

Two new sesquiterpene lactones, 6β‐hydroxy‐8α‐ethoxyeremophil‐7(11)‐en‐12,8β‐olide ( 1 ) and 4β,10β‐dihydroxy‐1αH,5αH,11αH‐guaian‐12,8β‐olide ( 2 ), together with 22 known sesquiterpenoids with various structural types, were isolated from Carpesium cernuum (Compositae). Their structures and configurations were elucidated by extensive 1D‐ and 2D‐NMR spectroscopic analysis in combination with MS experiments, and comparison with literature data of related compounds.     

Baimantuoluosides A – C,Three New Withanolide Glucosides from the Flower of Datura metel L.

In search for bioactive compounds from the flower of Datura metel L., three new withanolide glucosides, namely baimantuoluosides A, B, and C ( 1 – 3 , resp.) were isolated. Enzymatic hydrolysis of 1 – 3 afforded the corresponding aglycones 1a, 2a , and 3a , respectively. The structures of the new compounds were elucidated as (5α,6α,7α,12β,22R)‐5,12‐dihydroxy‐1,26‐dioxo‐6,7 : 22,26‐diepoxyergosta‐2,24‐dien‐27‐yl β‐D ‐glucopyranoside ( 1 ), (5α,6α,7α,12α,22R)‐5,12‐dihydroxy‐1,26‐dioxo‐6,7 : 22,26‐diepoxyergosta‐2,24‐dien‐27‐yl β‐D ‐glucopyranoside ( 2 ), (5α,6α,7α,22R)‐5‐hydroxy‐1,26‐dioxo‐6,7 : 22,26‐diepoxyergosta‐2,24‐dien‐27‐yl β‐D ‐glucopyranoside ( 3 ) on the basis of chemical and physicochemical evidence, and are further confirmed by the structure determination by X‐ray diffraction of withanolide aglycone 1a .     

Furostane‐Type Steroidal Saponins from the Roots of Chlorophytum borivilianum

Four new furostanol steroid saponins, borivilianosides A–D ( 1 – 4 , resp.), corresponding to (3β,5α,22R,25R)‐26‐(β‐D ‐glucopyranosyloxy)‐22‐hydroxyfurostan‐3‐yl O‐β‐D ‐xylopyranosyl‐(1→3)‐O‐β‐D ‐glucopyranosyl‐(1→4)‐O‐[α‐L ‐rhamnopyranosyl‐(1→2)]‐β‐D ‐galactopyranoside ( 1 ), (3β,5α,22R,25R)‐ 26‐(β‐D ‐glucopyranosyloxy)‐22‐methoxyfurostan‐3‐yl O‐β‐D ‐xylopyranosyl‐(1→3)‐O‐β‐D ‐glucopyranosyl‐(1→4)‐O‐[α‐L ‐rhamnopyranosyl‐(1→2)]‐β‐D ‐galactopyranoside ( 2 ), (3β,5α,22R,25R)‐26‐(β‐D ‐glucopyranosyloxy)‐22‐methoxyfurostan‐3‐yl O‐β‐D ‐xylopyranosyl‐(1→3)‐O‐[β‐D ‐glucopyranosyl‐(1→2)]‐O‐β‐D ‐glucopyranosyl‐(1→4)‐β‐D ‐galactopyranoside ( 3 ), and (3β,5α,25R)‐26‐(β‐D ‐glucopyranosyloxy)furost‐20(22)‐en‐3‐yl O‐β‐D ‐xylopyranosyl‐(1→3)‐O‐[β‐D ‐glucopyranosyl‐(1→2)]‐O‐β‐D ‐glucopyranosyl‐(1→4)‐β‐D ‐galactopyranoside ( 4 ), together with the known tribuluside A and (3β,5α,22R,25R)‐26‐(β‐D ‐glucopyranosyloxy)‐22‐methoxyfurostan‐3‐yl O‐β‐D ‐xylopyranosyl‐(1→2)‐O‐[β‐D ‐xylopyranosyl‐(1→3)]‐O‐β‐D ‐glucopyranosyl‐(1→4)‐O‐[α‐L ‐rhamnopyranosyl‐(1→2)]‐β‐D ‐galactopyranoside were isolated from the dried roots of Chlorophytum borivilianum Sant and Fern . Their structures were elucidated by 2D ‐NMR analyses (COSY, TOCSY, NOESY, HSQC, and HMBC) and mass spectrometry.     

Two New Steroidal Saponins from the Fresh Leaves of Agave sisalana

A new furostanol saponin, sisalasaponin C ( 1 ), and a new spirostanol saponin, sisalasaponin D ( 2 ), were isolated from the fresh leaves of Agave sisalana, along with three other known steroidal saponins and two stilbenes. Their structures were identified as (3β,5α,6α,22α,25R)‐3,26‐bis[(β‐D ‐glucopyrano‐ syl)oxy]‐22‐hydroxyfurostan‐6‐yl β‐D ‐glucopyranoside ( 1 ), (3β,5α,25R)‐12‐oxospirostan‐3‐yl 6‐deoxy‐α‐L ‐mannopyranosyl‐(1→4)‐β‐D ‐glucopyranosyl‐(1→3)‐[β‐D ‐xylopyranosyl‐(1→3)‐β‐D ‐glucopyranosyl‐(1→2)]‐β‐D ‐glucopyranosyl‐(1→4)‐β‐D ‐galactopyranoside ( 2 ), (3β,5α,6α,22α,25R)‐22‐methoxyfurostane‐3,6,26‐triyl tris‐β‐D ‐glucopyranoside, cantalasaponin‐1, polianthoside D, (E)‐ and (Z)‐2,3,4′,5‐tetrahydroxystilbene 2‐O‐β‐D ‐glucopyranosides. The last three known compounds were isolated from the fresh leaves of Agavaceae for the first time. The structures of the new compounds were elucidated by detailed spectroscopic analysis, including 1D‐ and 2D‐NMR experiments, and chemical techniques.     

Three New Atisane Diterpenoids from Spiraea japonica

Three new atisane diterpenoids, spiratisanins A – C ( 1  –  3 , resp.), featuring a phenylacryloxyl substituted ent‐atisane skeleton, were isolated from Spiraea japonica together with two known atisine diterpene alkaloids, spiramine A ( 4 ) and spiradine F ( 5 ). The structures of these new compounds were elucidated as (5β,7α,8α,9β,10α,12α,16β)‐16‐hydroxyatisan‐7‐yl (2E)‐3‐phenylprop‐2‐enoate ( 1 ), (5β,7α,8α,9β,10α,12α,16α)‐16‐hydroxyatisan‐7‐yl (2E)‐3‐phenylprop‐2‐enoate ( 2 ), and (5β,8α,9β,10α,12α,16β)‐16‐hydroxyatisan‐20‐yl (2E)‐3‐phenylprop‐2‐enoate ( 3 ) on the basis of spectroscopic analysis.     

Synthesis of Four Spacer-Containing Trisaccharides with the 4-0-(β-L-Rhamnopyranosyl)-D-glucopyranose Unit in Common,Representing Fragments of Capsular Polysaccharides from Streptococcus Pneumoniae Types 2, 7F, 22F,and 23F

Abstract

The synthesis is reported of 3-aminopropyl 3-O-[4-O(β-L-rhamnopyranosyl)-β-D-glucopyranosyl]-α-L-rhamnopyranoside (34), 3-aminopropyl 2-acetamido-3-O-[4-0-(β-L-rhamnopyranosyl)-β-D-glucopyranosyl]-2-deoxy-β-D-galactopyranoside (37), 3-aminopropyl 3-O-[4-O-(β-L-rhamnopyranosyl)-α-D-glucopyranosyl]-α-D-galactofuranoside (41), and 3-aminopropyl 4-O-[4-O-(β-L-rhamnopyranosyl)-β-D-glucopyranosyl]-β-D-galactopyranoside (45). These are spacer-containing fragments of the capsular polysaccharides of Streptococcus pneumoniae type 2, 7F, 22F, and 23F, respectively, which are constituents of Pneumovax^© 23. 2,3,4-Tri-O-benzyl-α-L-rhamnopyranosyl bromide was coupled to l,6-anhydro-2,3-di-(O-benzyl-β-D-glucopyranose (3). Opening of the anhydro ring, removal of AcO-1, and imidation of l,6-anhydro-2,3-di- O-benzyl-4-O-(2,3,4-tri-O-benzyl-β-L-rhamnopyranosyl)-β-D-glucopyranose (4β) afforded 6-O-acetyl-2,3-di-O-ben-zyl-4-O-(2,3,4-tri- O-benzyl-β-L-rhamnopyranosyl)-αβ-D-glucopyranosyl trichloroacet-imidate (7αβ). Condensation of 7αβ with 3-N-benzyloxycarbonylaminopropyl 2-O-ben-zyl-5,6-O-isopropylidene-α-D-galactofuranoside (26), followed by deprotection gave 41 Opening of the anhydro ring of 4 p followed by debenzylation, acerylauon, removal of AcO-1, and imidation yielded 2,3,6-tri-(9-aceryl-4-O-(2,3,4-tri-0-acetyl-P-L-rharnnopyran-.-osyl)-α-D-glucopyranosyl trichloroacetimidate (11). Condensation of 11 with 3-N-bcn-zyloxycarbonylaminopropyl 2,4-di-O-benzyl-α-L-rhamnopyranoside (18), with 3-N-bcn-zyloxycarbonylaminopropyl 2-acetamido-4,6-O-benzylidene-2-deoxy-β-D-galactopyran-oside (21), or with 3-N -benzyloxycarbonylaminopropyl 2-O-acetyl-3-O-allyl-6-O-benzyl-β-D-galactopyranoside (31), followed by deprotection afforded 34, 37, and 45, respectively.     

New Furostanol Glycosides from the Roots of Digitalis ciliata Trautv.

Three new furostanol glycosides, named ciliatasides A, B, and C ( 1 – 3 , resp.), have been isolated from the roots of Digitalis ciliata, along with two known furostanol glycosides. The structures of the new compounds were identified as (2α,3β,5α,14β,25R)‐26‐(β‐D ‐glucopyranosyloxy)‐2‐hydroxyfurost‐20(22)‐en‐3‐yl β‐D ‐glucopyranosyl‐(1→2)‐[β‐D ‐glucopyranosyl‐(1→3)]‐β‐D ‐galactopyranoside ( 1 ), (2α,3β,5α,14β,22R)‐26‐(β‐D ‐glucopyranosyloxy)‐2‐hydroxy‐22‐methoxyfurost‐25(27)‐en‐3‐yl β‐D ‐galactopyranosyl‐(1→2)‐[β‐D ‐xylopyranosyl‐(1→3)]‐β‐D ‐glucopyranosyl‐(1→4)‐β‐D ‐galactopyranoside ( 2 ), and (2α,3β,5α,14β,22R,25R)‐26‐(β‐D ‐glucopyranosyloxy)‐2,22‐dihydroxyfurostan‐3‐yl β‐D ‐glucopyranosyl‐(1→2)‐[β‐D ‐glucopyranosyl‐(1→3)]‐β‐D ‐galactopyranoside ( 3 ).     

Four New Compounds from Sinacalia tangutica

Four new compounds, 9α‐hydroxy‐1β‐methoxycaryolanol ( 1 ), stigmast‐5‐ene‐7α,22α‐diol‐3β‐tetradecanoate ( 2 ), 7‐O‐(6′‐acetoxy‐β‐D ‐glucopyranosyl)coumarin ( 3 ), and 8‐O‐(6′‐acetoxy‐β‐D ‐glucopyranosyl)‐7‐hydroxycoumarin ( 4 ), together with ten known compounds, were isolated from the aerial parts of Sinacalia tangutica. The structures of the new compounds were established by means of extensive spectroscopic analyses (1D‐ and 2D‐NMR, EI‐MS, HR‐ESI‐MS, as well as IR and UV) and by comparison of their spectroscopic data with those of structurally related compounds reported in the literature.     

Withanolides from Aureliana fasciculata var. fasciculata

In the first phytochemical study of the Aureliana genus (Solanaceae), two new withanolides, 1 and 2 , together with two known sterols, were isolated from the MeOH extract of the leaves of Aureliana fasciculata var. fasciculata. The structures were established as (4S,22R)‐16α‐acetoxy‐5β,6β‐epoxy‐4β,17α‐dihydroxy‐1‐oxowitha‐2,24‐dienolide (aurelianolide A) and (4S,22R)‐16α‐acetoxy‐4β,17α‐dihydroxy‐1‐oxowitha‐2,5,24‐trienolide (aurelianolide B). The new compounds possessed the unusual 16α,17α‐dioxygenated group and were fully characterized by spectroscopic techniques, including ¹H‐ and ¹³C‐NMR (DEPT), as well as 2D‐NMR (HMBC, HMQC, ¹H,¹H‐COSY, NOESY) experiments, and HR‐MS.