Structure and Absolute Configuration of Aspergilumamide A,a Novel Lumazine Peptide from the Mangrove‐Derived Fungus Aspergillus sp.

A novel lumazine peptide, aspergilumamide A ( 1 ), as well as a known analog penilumamide ( 2 ), were isolated from the mycelia of a marine‐derived fungus Aspergillus sp. (33241), obtained from the mangrove Bruguiera sexangula var. rhynchopetala collected from the South China Sea. The structure of 1 was identified by comprehensive spectroscopic analysis, including 1D‐ and 2D‐NMR, ESI‐MS, and MS/MS experiments. The absolute configuration of 1 was determined by Marfey's method.     

A New Glycine Derivative and a New Indole Alkaloid from the Fermentation Broth of the Plant Endophytic Fungus Pestalotiopsis podocarpi Isolated from the Chinese Podocarpaceae Plant Podocarpus macrophyllus

A new glycine derivative, podocarpiamide ( 1 ), a new indole alkaloid, 1‐methoxy‐1H‐indol‐3‐ethanol ( 2 ), together with two known compounds, 1‐methoxy‐1H‐indole‐3‐acetic acid ( 3 ) and methyl 1‐methoxy‐1H‐indole‐3‐acetate ( 4 ), were isolated from the fermentation broth of the plant endophytic fungus Pestalotiopsis podocarpi. Their structures were elucidated by extensive spectroscopic analysis including 1D‐ and 2D‐NMR (HSQC, HMBC, and COSY) and MS experiments. Compound 1 has an interesting unusual carbamic acid structure.     

Polyhydroxypregnane Glycosides from the Roots of Cynanchum otophyllum

Six new polyhydroxypregnane glycosides, namely cynotophyllosides A–F ( 1 – 6 ), together with five known steroids, were isolated from the roots of Cynanchum otophyllum. Their structures were elucidated by extensive spectroscopic methods (especially 2D‐NMR techniques) and acid‐catalyzed hydrolysis. Furthermore, high field 1D‐ and 2D‐NMR experiments were employed to elucidate the structure of 8 previously deduced only on the basis of LC/MS data.     

Tuberculariols A – C,New Sesquiterpenes from the Mutant Strain M‐741 of Tubercularia sp. TF5

Three new sesquiterpenes, tuberculariols A–C ( 1 – 3 , resp.), were isolated from the mutant strain M‐741 of Tubercularia sp. TF5, an endophytic fungus of Taxus mairei. Their structures were elucidated by spectroscopic analyses including 1D‐ and 2D‐NMR experiments, and HR‐Q‐TOF‐MS. Antitumor and antibacterial properties of these compounds were evaluated.     

Eremophilane‐Type Sesquiterpenoids from the Fermentation Broth of Plant Endophytic Fungus Pestalotiopsis photiniae Isolated from the Chinese Podocarpaceae Plant Podocarpus macrophyllus

Two new sesquiterpenoid esters, pestalotiopins B and C ( 1 and 2 , resp.) related to the eremophilane class, together with one known compound, berkleasmin C ( 3 ), were isolated from the fermentation broth of the plant endophytic fungus Pestalotiopsis photiniae. Their structures and relative configurations were elucidated by extensive spectroscopic analysis including 1D‐ and 2D‐NMR (HSQC, HMBC, and NOESY), and MS experiments. Compound 1 has an interesting lactam structure, and this type of sesquiterpenoid with a lactam structure is reported for the first time.     

Constituents of the Endophytic Fungus Annulohypoxylon boveri var. microspora BCRC 34012

A new azaphilone metabolite with a new substitution pattern, named annulohypoxylin ( 1 ), together with twelve known compounds, were isolated from the BuOH‐soluble fraction of the 95% EtOH extract of long‐grain rice (Oryza sativa) fermented with the endophytic fungus Annulohypoxylon boveri var. microspora (BCRC 34012). Annulohypoxylin ( 1 ) contains a dihydrobenzofuran‐2,4‐dione backbone, 1‐hydroxyoctyl side chain, and one γ‐lactone ring. Its structure was determined on the basis of extensive 1D‐ and 2D‐NMR analyses in combination with HR‐ESI‐MS. The relative configuration of 1 was confirmed by NOESY experiment. Other known compounds were identified by comparing their spectral data with those in the literature. All known compounds were isolated from this species for the first time.     

New Cytochalasins from the Marine‐Derived Fungus Xylaria sp. SCSIO 156

Two new cytochalasins, 18‐deoxycytochalasin Q ( 1 ) and 21‐O‐deacetylcytochalasin Q ( 2 ), together with four known analogues, cytochalasin Q ( 3 ), 19,20‐epoxycytochalasin Q ( 4 ), 21‐O‐deacetyl‐19,20‐epoxycytochalasin Q ( 5 ), and cytochalasin D ( 6 ), were isolated from the fungus Xylaria sp. SCSIO156 originated from the South China Sea marine sediment. The structures of 1 and 2 were elucidated by MS and 1D‐ and 2D‐NMR data analyses, and comparison with known compounds. The known compounds 3 – 6 were identified by comparison of their MS and NMR data with those reported in the literature. In the in vitro antitumor assay, compounds 2 – 6 showed mild cytotoxicity against three tumor cell lines (MCF‐7, SF‐268, and NCI‐H460).     

Palmarumycins from the Endophytic Fungus Lasiodiplodia pseudotheobromae XSZ‐3

One new and three known spiro‐dioxynaphthalene compounds, related to palmarumycins, were isolated from the extracts of fungus Lasiodiplodia pseudotheobromae XSZ‐3. Their structures were established by spectroscopic methods (1D‐ and 2D‐NMR, HR‐ESI‐MS, etc.). The absolute configuration of 1 was determined by comparison of quantum‐chemical TDDFT (time‐dependent density‐functional theory) calculated and experimental ECD (electronic circular dichroism) spectra. The cytotoxic activities of 1 – 4 against HL‐60 cell line were evaluated by trypan blue‐staining assay.     

Dicitrinol,a Citrinin Dimer,Produced by Penicillium janthinellum

A citrinin dimer, named dicitrinol ( 3 ), was isolated from extracts obtained from a rice cultivation of Penicillium janthinellum, a fungus found in fruits of Melia azedarach. Dicitrinol ( 3 ) was isolated by classical chromatographic procedures, and identified by MS, and 1D‐ and 2D‐NMR data. A biosynthetic scheme is proposed for this new dimerization of citrinin. Dicitrinol ( 3 ) was shown to be slightly weaker than citrinin regarding bacterial inhibition.     

Cottoquinazolines E and F from Neosartorya fischeri NRRL 181

Two new norfumiquinazolines, cottoquinazolines E and F ( 1 and 2 , resp.), together with pyripyropene A ( 3 ), were isolated from the fungus Neosartorya fischeri NRRL 181. The structures of the new isolates were established by spectroscopic methods, including UV, IR, HR‐ESI‐MS, and extensive 1D‐ and 2D‐NMR techniques. To the best of our knowledge, this is the first report on norfumiquinazolines and pyripyropenes produced by the genus Neosartorya.     

Trichocarpinine,a Novel Hetidine–Hetisine Type Bisditerpenoid Alkaloid from Aconitum tanguticum var. trichocarpum

Trichocarpinine ( 1 ), the first hetidine–hetisine type bisditerpenoid alkaloid, was isolated from the whole herbs of Aconitum tanguticum var. trichocarpum. Its structure was determined by a combination of spectroscopic techniques, including HR‐ESI‐MS and 1D‐ and 2D‐NMR experiments. Its plausible biogenetic pathway was proposed as well (Scheme).     

A New Dimeric Secoiridoid Glycoside from the Leaves of Olea ferruginea Royle

A new dimeric secoiridoid glycoside, trivially named oleferrugine B ( 1 ), has been isolated from the AcOEt‐soluble part of the MeOH extract of leaves of Olea ferruginea Royle . The structure of the isolated compound was established on the basis of ESI‐MS fragmentation patterns, and 1D‐ and 2D‐NMR techniques, including ¹H‐ and ¹³C‐NMR, HSQC, ¹H,¹H‐COSY, HMBC, and NOESY experiments, and by comparison with literature data.     

Two New Octahydronaphthalene Derivatives from Trichoderma spirale,an Endophytic Fungus Derived from Aquilaria sinensis

Two new octahydronaphthalene derivatives, trichodermic acid A ( 1 ) and trichodermic acid B ( 2 ), along with a known analog, trichodermic acid ( 3 ), and a known modified dipeptide, trichodermamide A ( 4 ), were isolated from the extract of Trichoderma spirale, an endophytic fungus present in the medicinal plant Aquilaria sinensis. The structures of these compounds were established by extensive analysis of their spectroscopic data including 1D‐ and 2D‐NMR and MS data.     

Floccosic Acid,a New Triterpenic Acid from Nepeta floccosa

The isolation and structure elucidation of a new triterpenic acid named floccosic acid ( 1 ) is reported on the basis of the 1D‐ and 2D‐NMR assignments. This secondary metabolite was isolated as a new constituent, along with the known triterpenoids, betulinic acid and β‐amyrin. All these compounds were purified by repeated column chromatography of the MeOH extract of Nepeta floccosa. The structure elucidation of the new compound was accomplished by the combined mass spectrometry (MS), infrared (IR) and ultraviolet (UV) absorption spectroscopy, one‐ (¹H‐ and ¹³C‐) and two‐dimensional (H? C correlations; HMBC and HSQC) NMR techniques. The known compounds were identified by comparison of their physical and spectroscopic data with those reported in the literature.     

Furanone Derivatives from Aspergillus sp. XW‐12, an Endophytic Fungus in Huperzia serrata

Two new 5‐methoxyfuran‐3(2H)‐one derivatives, huaspenone A ( 1 ) and B ( 2 ), together with four known ones, i.e., aspertetronin A ( 3 ), aspertetronin B ( 4 ), gregatin E ( 5 ), and penicilliol A ( 6 ), were isolated from the cultures of an endophytic fungus Aspergillus sp. XW‐12, derived from the stems of Huperzia serrata. The structures of the new isolates were established by detailed interpretation of the 1D‐ and 2D‐NMR and HR‐ESI‐MS data.     

A Novel 19,21‐Secohetisan Diterpenoid Alkaloid from Aconitum tanguticum

A novel 19,21‐secohetisan diterpenoid alkaloid, tangutisine A ( 1 ), was isolated from Aconitum tanguticum (Maxim .) Stapf . Its structure was determined by HR‐EI‐MS and 1D‐ and 2D‐NMR spectroscopy and by comparison with the data of known 19,21‐secohetisan derivatives.     

Ophiobolin Sesterterpenoids and Pyrrolidine Alkaloids from the Sponge‐Derived Fungus Aspergillus ustus

Chemical examination of the fungus Aspergillus ustus isolated from the Mediterranean sponge Suberites domuncula yielded the five new ophiobolin‐type sesterterpenoids 1 – 5 and the two new pyrrolidine alkaloids 6 and 7 , together with the known compound aurantiamine and cerebroside D. The structures of the new compounds were unambiguously elucidated on the basis of extensive spectroscopic‐data analysis (1D‐ and 2D‐NMR, MS, and UV) and comparison with literature data. All compounds were evaluated for their cytotoxicity against murine lymphoma cell line L5178Y.     

Spectral study of a new dihydroisocoumarin

A novel dihydroisocoumarin, 3,4‐dihydro‐6,8‐dihydroxy‐3‐(2′‐acetyl‐3′‐hydroxy‐5′‐methoxy)methyl‐1H‐[2]benzopyran‐1‐one, was isolated from the chloroform extract of the sap of the traditional herb Aloe vera. Its structure was determined by high‐resolution negative fast atom bombardment mass spectrometry (MS), 2D NMR spectroscopy and x‐ray crystallography. The molecular structure was elucidated by 2D NMR analysis. The complete assignment of the ¹H and ¹³C NMR spectra of this compound was performed by using ¹H detected one‐bond heteronuclear multiple quantum correlation (HMQC) and long‐range (two and three bonds) heteronuclear multiple quantum bond correlation (HMBC) experiments. Detailed analyses of the one‐ and two‐dimensional NMR techniques are presented in additional to the spectral properties (MS, IR and UV). Copyright © 2003 John Wiley & Sons, Ltd.     

Hemsleyaconitines F and G,Two Novel C19‐Diterpenoid Alkaloids Possessing a Unique Skeleton from Aconitum hemsleyanum

Hemsleyaconitines F and G ( 1 and 2 , resp.) were isolated from the EtOH extract of Aconitum hemsleyanum. Their structures were elucidated by extensive analyses of the IR, 1D‐ and 2D‐NMR, and MS data. The two C₁₉‐diterpenoid alkaloids 1 and 2 possess a novel skeleton, featuring a five‐membered D‐ring between C(9), C(13), C(14), C(15), and C(16), which is quite different from the previously isolated six‐membered D‐ring analogs.     

Piepunine,A Novel Bis‐diterpenoid Alkaloid from the Roots of Aconitum piepunense

Further investigation on the roots of Aconitum piepunense led to the isolation of a novel bis‐diterpenoid alkaloid designated as piepunine ( 1 ). Its structure was established by extensive interpretation of its 1D‐ and 2D‐NMR data, high‐resolution ESI‐MS, and IR spectra. Piepunine represents the first example of an atisine–denudatine‐type bis‐diterpenoid alkaloids.