Terpenoids from endophytic fungi

This work reviews the production of terpenoids by endophytic fungi and their biological activities, in period of 2006 to 2010. Sixty five sesquiterpenes, 45 diterpenes, five meroterpenes and 12 other terpenes, amounting to 127 terpenoids were isolated from endophytic fungi.     

Terpenoids from Loxocalyx urticifolius

Two new diterpenoids, loxocalyxin A ( 1 ) and 13‐epiloxocalyxin A ( 2 ), and two new sesquiterpenoids, loxocalyxins B and C ( 3 and 4 , resp.), together with three known compounds, were isolated from the MeOH extract of the whole plant of Loxocalyx urticifolius Hemsl . The structures of the new compounds were established by means of spectroscopic analysis including one‐ and two‐dimensional NMR spectroscopy. All new structures were confirmed by X‐ray crystallographic analysis. Their absolute configurations were established.     

Terpenoids from Croton regelianus

Two new terpenoids, the bisnorditerpene rel‐(5β,8α,10α)‐8‐hydroxy‐13‐methylpodocarpa‐9(11),13‐diene‐3,12‐dione ( 1 ) and the guaiane sesquiterpene rel‐(1R,4S,6R,7S,8aR)‐decahydro‐1‐(hydroxymethyl)‐4,9,9‐trimethyl‐4,7‐(epoxymethano)azulen‐6‐ol ( 2 ), together with seven known compounds, were isolated from Croton regelianus var. matosii. The structures of the isolated compounds were determined by HR‐ESI‐TOF and a combination of 1D‐ and 2D‐NMR experiments.     

Terpenoids from Chloranthus multistachys

Two new diterpenoids, ent-17-hydroxyl-16beta-methoxyl-kauran-3-one (1) and ent-17-acetoxyl-16beta-methoxyl-kauran-3-one (2), along with nine known compounds (3-12), ent-17-hydroxyl-kaur-15-en-3-one (3), ent-3beta-acetoxyl-kaur-15-en-16beta, 17-diol (4), ent-kauran-3beta, 16beta, 17-triol (5), ent-3beta-acetoxyl-kauran-16beta, 17-diol (6), ent-kauran-16beta, 17-diol (7), abbeokutone (8), ent-17alpha-acetyl-16beta-hydroxyl- kauran-3-one (9), shizukaol F (10), cycloshizukaol A (11) and curcolonol (12), were isolated from Chloranthus multistachys (Chloranthaceae). Their structures were elucidated by spectroscopic spectra.     

Alkaloids from the stem bark of Turraeanthus africanus (Meliaceae)

Fractionation of the methanol extract of the stem bark of Turraeanthus africanus led to the isolation of two new alkaloids designated turraeanthin A and B, together with two known alkaloids. The structures of the new alkaloids were elucidated by means of spectroscopic analysis and characterized as 10-O-demethyl-17-O-methyl isoarnottianamide and 11-demethoxyl-12-methoxyl oxynitidine respectively.     

Studies of the constituents of Gardenia species. II. Terpenoids from Gardeniae Fructus

Four new terpenoids, gardenate A (1), 2-hydroxyethyl gardenamide A (2), (1R,7R,8S,10R)-7,8,11-trihydroxyguai-4-en-3-one 8-O-beta-D-glucopyranoside (3) and Jasminoside F (4), were isolated from Gardeniae Fructus. Their structures were established on the basis of spectral analysis.     

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.     

Terpenoids from Eupatorium fortunei Turcz

Four new terpenoids, namely, rel‐(1R,2S,3R,4R,6S)‐p‐menthane‐1,2,3,6‐tetrol ( 1 ), rel‐(1R,2R,3R,4S,6S)‐p‐menthane‐1,2,3,6‐tetrol ( 2 ), 9‐hydroxythymol 3‐O‐angelate ( 3 ), and (3β,20R)‐20‐hydroxylanost‐25‐en‐3‐yl palmitate ( 4 ), together with fourteen known compounds, were isolated from the AcOEt part of the MeOH extracts of Eupatorium fortunei. In addition, two other monoterpenoids, ‘acetone thymol‐8,9‐diyl ketal’ ( 19 ) and 8‐methoxy‐9‐hydroxythymol 3‐O‐angelate ( 20 ) were also obtained which were probably artifacts but have never been reported in the literature. The structures of the new compounds, including their relative configurations, were established by an extensive study of their spectral data, especially 1D‐ and 2D‐NMR. The cytotoxic activity of the new compounds against human hepatoma (SMMC‐7721), human leukemia (HL‐60), and human hepatocyte (LO₂) cells was investigated.     

Cytotoxic Terpenoids from Turraea pubescens

Three new triterpenoids, turrapubesols A–C ( 1 – 3 ), and one new sesquiterpenoid, 1α,4α‐dihydroxyeudesman‐11‐ene ( 4 ), along with 12 known terpenoids were isolated from Turraea pubescens. The structures of the terpenoids were established on the basis of extensive spectroscopic analyses and by a chemical transformation. The previous assignment of the NMR data for guaidiol ( 5 ) was corrected. Some of the triterpenoids exhibited cytotoxicity against the P‐388 cell line.     

Three New Terpenoids from Pinus yunnanensis

A new abietatrienoid, 15‐methoxydidehydroabietic acid ( 1 ), a new ring B‐seco abietatrienoid, 10‐hydroxy‐9,10‐secoabieta‐8,11,13‐trien‐18‐oic acid ( 2 ), and a new tetracyclic triterpenoid, pinusyunnanol ( 3 ), together with five known compounds, were obtained from the twigs and needles of Pinus yunnanensis. The structures of the new compounds were elucidated by means of extensive spectroscopic analyses.     

Terpenoids from Roots of Chloranthus spicatus

Five new terpenoids, including four eudesmane‐type sesquiterpenoids, 1 – 4 , and one labdane‐type diterpenoid, 6 , together with ten known compounds, were isolated from the roots of Chloranthus spicatus. The structures and their relative configurations were mainly established by 1D‐ and 2D‐NMR spectra, and MS experiments.     

Terpenoids from the Plant Ferula ferganensis

Chemistry of Natural Compounds -     

New Terpenoids from Basidiomycetes Russula lepida

Three new triterpenoids and two new aristolane sesquiterpenoids, namely (24E)‐3β‐hydroxycucurbita‐5,24‐diene‐26‐oic acid ( 1 ), (24E)‐3,4‐secocucurbita‐4,24‐diene‐3,26‐dioic acid ( 4 ), (24E)‐3,4‐secocucurbita‐4,24‐diene‐3,26,29‐trioic acid ( 5 ), rulepidadiol ( 6 ), and rulepidatriol ( 7 ), were isolated from the fruiting bodies of Basidiomycetes Russula lepida. Their structures were established by spectral methods. Acids 4 , and 5 are the first examples of naturally occurring seco‐ring‐A cucurbitane triterpenoids. Alcohols 6 and 7 , belonging to the aristolane‐type sesquiterpenoids, are of a type rather rare in nature, especially among fungal species.     

Terpenoids and aromatic compounds from the New Zealand liverworts Plagiochila, Schistochila, and Heteroscyphus species

A new clerodane- and two new ent-rosane-type diterpenoids have been isolated from the New Zealand liverworts Heteroscyphus billardierii and Plagiochila deltoidea, respectively. The known bisbibenzyl compounds and acetophenones have also been isolated from Schistochila glaucescens and Plagiochila fasciculata. Their structures were established by extensive NMR techniques. Chemosystematics of the Plagiochila species have been discussed.     

Terpenoids from the Chinese Liverwort Chiloscyphus polyanthus

A new diterpene, (7α,11β,14β,16R)‐7,11,14‐trihydroxy‐ent‐kaur‐15‐one ( 1 ), and a new sesquiterpene, polyanthuslide ( 2 ), were isolated from the Chinese liverwort Chiloscyphus polyanthus. Their structures were determined on the basis of extensive spectroscopic analyses, and the configuration of 2 was established by X‐ray crystallographic analysis.     

萜类化合物为手性源合成拒食剂研究进展

总结了近年来国内外一些萜类化合物如环柠檬醛、香芹酮、香茅醇、紫苏醇、蒈烯、苎烯和环香叶醇等作为手性源在立体选择性合成拒食剂方面的新进展,并且对合成方法进行了简单介绍。最后对萜类化合物在合成拒食剂方面的应用进行了展望。