Drimane Sesquiterpenoids Research Articles

New Drimane Sesquiterpenoids from Tidestromia Oblongifolia

From an acetone extract of the aerial parts of Tidestromia oblongifolia (Amaranthaceae), a new drimane sesquiterpenoid bearing an 11,12,13-trihydroxydrimene skeleton (1) as well as the 11,12 acetonide of 1 were isolated. Three known stigmastane triterpenoids were also isolated. Structures were elucidated with the aid of 1D and 2D NMR spectroscopic techniques. The absolute configuration of 1 was confirmed by single-crystal x-ray crystallography. This is the first report on phytochemical constituents from any plant of the genus Tidestromia and is the first report of the occurrence of drimanes in the Amaranthaceae.

Two Drimane-type Sesquiterpenes, Strobilactones A and B, from the Liquid Culture of the Edible Mushroom Strobilurus ohshimae

Two novel drimane sesquiterpenoids, strobilactones A (3) and B (4), were isolated fromthe organic extract of a liquid culture of Strobilurus ohshimae. The structures of 3 and 4 were determined by spectroscopic methods. Compounds 3 and 4 exhibit cell growth inhibitory activities against cultured COLO 201 cells. Compound 4 also shows antimicrobial activity against Staphylococcus aureus and Pseudomonas aeruginosa.

Inhibition of mycobacterial arylamine N-acetyltransferase contributes to anti-mycobacterial activity of Warburgia salutaris

In this study, we show that extracts and a purified compound of Warburgia salutaris exhibit anti-mycobacterial activity against Mycobacterium tuberculosis H37Rv and Mycobacterium bovis BCG Pasteur. The extracts did not inhibit growth of Escherichia coli and were not toxic to cultured mammalian macrophage cells at the concentrations at which anti-mycobacterial activity was observed. The extract and pure compound inhibited pure recombinant arylamine N-acetyltransferase (NAT), an enzyme involved in mycobacterial cell wall lipid synthesis. Moreover, neither extract nor pure compound inhibited growth of a strain of M. bovis BCG in which nat has been deleted suggesting that NAT may indeed be a target within the mycobacterial cell. The purified compound is a novel drimane sesquiterpenoid lactone, 11α-hydroxycinnamosmolide. These studies show that W. salutaris is a useful source of anti-tubercular compounds for further analysis and supports the hypothesis of a link between NAT inhibition and anti-mycobacterial activity.

Novel oxygenated meroterpenoids and drimane sesquiterpenoids from the sponge-derived fungus Penicillium citreonigrum

In the course of our continuing search for bioactive metabolites from marine-derived fungi, we have investigated an isolate of Penicillium citreonigrum obtained from the Indonesian sponge Pseudoceratina purpurea (Carter). Besides novel drimane sesquiterpenes bearing close structural similarity to compounds previously described from a marine alga-derived fungus,1 we obtained a series of highly complex oxygenated meroterpenes exemplified by citreonigrin A. These novel compounds can be divided into different structural types, and are probably biogenetically derived from the “fungal meroterpenoid pathway“ leading to known fungal metabolites such as austin or paraherquonine.2 Details on the structures, their proposed biogenetic relation to previously described natural products, and their biological activity will be reported.

Cinnafragrins A−C, Dimeric and Trimeric Drimane Sesquiterpenoids from Cinnamosma fragrans, and Structure Revision of Capsicodendrin

Two new dimeric sesquiterpenoids and a new trimeric drimane sesquiterpenoid named cinnafragrins A-C (1-3), together with cinnamodial (4), D-mannitol, capsicodendrin (5), and a vitamin E analogue, delta-tocotrienol, were isolated from Cinnamosma fragrans, a Malagasy medicinal plant. The structures of the new compounds were determined on the basis of physical, chemical, and spectroscopic evidence. Capsicodendrin, previously isolated from Capsicodendron dinisii and tentatively suggested to be a tetramer of cinnamodial, was revised structurally as a mixture of C-12'-epimers of 12'-hydroxycinnafragrin B by extensive 2D NMR analysis and X-ray crystallography of the lactone derivative, cinnafragrolide (6). The chemosystematics of the family Canellaceae are discussed.

Nebularic Acids and Nebularilactones, Novel Drimane Sesquiterpenoids from the Fungus Lepista nebularis

AbstractFour (nor‐)drimane sesquiterpenoids, nebularic acids A (1) and B (2) and nebularilactones A (3) and B (4), were isolated from a cultured Lepista nebularis strain by bioassay‐guided chromatography, and their structures were elucidated by mass spectrometry and NMR spectroscopy. Nebularic acid A (1) and in particular nebularic acid B (2), which features an α,β‐epoxy carboxylate moiety, show antifungal and antibacterial activities. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

In vitro 5-lipoxygenase and anti-oxidant activities of Warburgia salutaris and drimane sesquiterpenoids

The purpose of this investigation was to determine the in vitro 5-lipoxygenase inhibitory and anti-oxidant activities of Warburgia salutaris . Aqueous and methanol extracts of the leaves of W . salutaris were obtained and subjected to the 5-lipoxygenase assay and the 2,2- diphenyl-1-picrylhydrazyl (DPPH) assay to determine their anti-inflammatory and anti-oxidant activities, respectively. Furthermore, drimane sesquiterpenoids, mukaadial and warburganal, isolated from the same plant, were subjected to the same biological tests. The methanol extract of the leaves of W . salutaris displayed promising in vitro anti-inflammatory activity with an IC 50 value below 33 μg ml -1 , while the aqueous extract of the same plant exhibited no activity in the same assay. The aqueous and methanol extracts of W . salutaris displayed promising anti-oxidant activities with IC 50 values of 34.43 + 0.74 μg ml -1 and 15.38 ± 0.20 μg ml -1 , respectively. The compounds mukaadial and warburganal displayed 5-lipoxygenase inhibitory activity and contribute to the in vitro anti-inflammatory activity of the crude extract of the same plant. Anti-oxidant activity of W . salutaris did not appear to be confined to the drimane sesquiterpenoids tested.

Total Synthesis of 3‐Hydroxydrimanes Mediated by Titanocene(III) — Evaluation of Their Antifeedant Activity.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Total Synthesis of 3‐Hydroxydrimanes Mediated by Titanocene(III) – Evaluation of Their Antifeedant Activity

AbstractWe describe the first synthesis of 3β‐hydroxydihydroconfertifolin (3) and 3β‐hydroxycinnamolide (4), together with improved procedures for the preparation of other 3‐hydroxydrimanes (2 and 5) scarce in nature. The key step was the titanocene(III)‐promoted cyclization of epoxypolyprenes, readily prepared from commercial polyenes. In this way, we confirm the viability of our procedure for the synthesis of drimane sesquiterpenoids with different functionalization patterns. We also report on the antifeedant activity of 2–5 against four insect species with different feeding ecologies. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

Occurrence, Biological Activity and Synthesis of Drimane Sesquiterpenoids

AbstractFor Abstract see ChemInform Abstract in Full Text.

Occurrence, biological activity and synthesis of drimane sesquiterpenoids.

In this review the names, structures and occurrence of all new drimanes and rearranged drimanes which have been published between January 1990 and January 2003 have been collected. Subjects that have been treated are biosynthesis, analysis, biological activities, with special attention to cytotoxic activity and antifeedant and insecticidal activity and mode of action. An important part of the review deals with the synthesis of drimanes. This part has been subdivided into syntheses by transformation of natural products, syntheses starting from chiral compounds obtained by enzymatic resolution, syntheses by cationic polyolefin cyclizations, syntheses from trans-decalones, syntheses by radical cyclizations and syntheses by cycloaddition reactions. The review contains about 350 references.

Synthesis of 5,6-dehydro-7-oxoisodrimenin from drim-8-en-7-one

The natural drimane sesquiterpenoid lactone 5,6-dehydro-7-oxoisodrimenin was synthesized from drim-8-en-7-one as well as from 7-oxoisodrimenin.

A New Drimane from the Heartwood of the Japanese Yew, Taxus Cuspidata

A new drimane sesquiterpenoid was isolated from the heartwood of the Japanese yew, Taxus cuspidata Sieb. et Zucc. Its structure was established as 1 g -acetoxyisodrimeninol (1 g -acetoxy-11,12-epoxy-7-drimen-11-ol, 1 ). This compound was gradually oxidized to give n -lactone (1 g -acetoxy-8-drimeno-11,12-lactone, 4 ).

Total synthesis of (-)-mniopetal E, a novel biologically intriguing drimane sesquiterpenoid.

We have achieved the total synthesis of (-)-mniopetal E, a drimane sesquiterpenoid which inhibits the reverse transcriptase of human immunodeficiency virus (HIV)-1. Our enantiospecific total synthesis of this target molecule in naturally occurring form commenced with a known 2,3-anhydro-D-arabinitol derivative, which was prepared using the Sharpless asymmetric epoxidation strategy. The key steps of our total synthesis were as follows: (1) a combination of highly stereocontrolled inter- and intramolecular Horner-Emmons carbon elongations for construction of a butenolide tethering a 1,2,4, 9-functionalized nona-5,7-diene moiety at the beta-carbon, (2) stereoselective thermal intramolecular Diels-Alder reaction of the thus-formed trienic compound, providing preferentially an endo-cycloadduct with the desired pi-facial selection, and (3) efficient transformation of the gamma-lactone moiety in the major cycloadduct to the gamma-hydroxy-gamma-lactone part in mniopetal E. Our total synthesis of (-)-mniopetal E established the unsettled absolute stereochemistry of the antibiotic.

A drimane sesquiterpenoid lactone from Warburgia salutaris

The stem bark of Warburgia salutaris collected in Zoutpansberg mountains yielded a new drimane sesquiterpenoid lactone, salutarisolide, along with four known drimane sesquiterpenoids warburganal, mukaadial, polygodial and isopolygodial. The structure of salutarisolide was fully characterized from its spectral data. The lactone is structurally related to muzigadial.

NOVEL AND BIOACTIVE METABOLITES OF WARBURGIA SALUTARIS INDIGENOUS TO THE NORTHERN PROVINCE, SOUTH AFRICA

The stem bark of Warburgia salutyaris (Bertol. F. Chiov.) collected in Zoutpansberg mountains, South Africa, yielded a new drimane sessquiterpenoidd lactone, salutarisolide, along with four known drimane sesquiterpenoids warburganal, mukaadial, polygodial and isopolygodial. The structure of salutarisolide was fully characterized from its spectral data. The lactone is structurally related to muzigadial. Keywords — Warburgia salutaris; Canellaceae; salutarisolide; warburganal; muzigadial; polygodial; isopolygodial; NMR; INAPT; NOE; COSY. Nig. J. Nat Prod. And Med. Vol.3 1999: 28-30

New terpenoid metabolites from the skin extracts, an egg mass, and dietary sponges of the Northeastern Pacific dorid nudibranch Cadlinaluteomarginata

Chemical investigations of Cadlinaluteomarginata skin extracts, egg masses, and dietary sponges have led to the identification of the novel terpenoids cadlinaldehyde (30), spongian 32, seco-spongian 35, 20-acetoxy-12-marginatone (38), and lutenolide (39) from the nudibranch skin extracts, the new drimane sesquiterpenoid 1α,2α-diacetoxyalbicanyl acetate (40) from the nudibranch's egg mass, and the new sesquiterpenoids O-methyl-9-oxofurodysininlactone (47), 2-oxomicro-cionin-2-lactone (48), and O-methyl-2-oxomicrocionin-2-lactone (49), from the dietary sponge Pleraplysilla sp. The known terpenoids furodysinin (1), furodysin (16), marginatafuran (21), and 9,11-dihydrogracillin A (37), which have been frequently isolated from C. luteomarginata skin extracts, were found for the first time in extracts of the dietary sponges Pleraplysilla sp. and Aplysilla sp. One of the new terpenoids, cadlinaldehyde (30), has an unprecedented degraded sesterterpenoid skeleton. Keywords: nudibranch, sponge, terpenoids, structure elucidation.

Sesquiterpenoids from a Cell Suspension Culture of the LiverwortPorella vernicosa Lindb

The liverwort Porella vernicosa Lindb. was cultured in vitro in Murashige and Skoog's medium. The pungent sesquiterpene dialdehyde, polygodial, was found as the major metabolite (20.3%). The second major metabolite was norpinguisone methyl ester (18.7%). In addition β-bisabolene (12.7%), drimenol (8.4%), cyclocolorenone (7.5%) and other drimane and pinguisane sesquiterpenoids were identified by GC-MS analysis. In the field-grown liverwort, the major metabolite was norpinguisone (24.5%) accompanied by polygodial (21.7%) and cyclocolorenone (13.4%). Thus the content of polygodial in the mixture of metabolites produced by P. vernicosa cultured in vitro was similar to that in the field-grown plant.

Synthesis of drim-8(9)-en-7-one, drima-5,8(9)-dien-7-one, and their 11,12-dibromo derivatives from norambreinolide

A method was elaborated for the synthesis of polyfunctional compoonds of the drimane series,viz., drim-8(9)-en-7-one, drima-5,8(9)-dien-7-one, and their 11,12-dibromo derivatives, potential intermediates for the synthesis of natural biologically active drimane sesquiterpenoids starting from norambreinolide. The key intermediate of the above drimane compounds is methyl 7-oco-11-homodrim-8(9)-en-12-oate, prepared by electrochemical oxidation of a mixture of isomeric methyl bicyclohomofarnesenoates obtained from norambreinolide.

Stereoselective Synthesis of (+)-Avarol, (+)-Avarone, and Some Nonracemic Analogues.

Synthesis of the rearranged drimane sesquiterpenoids (+)-avarol and (+)-avarone from Wieland-Miescher ketone is described. This synthetic sequence provides convenient access to the natural enantiomers and, based on comparison of the optical rotation of synthetic avarol dimethyl ether with literature data, affords material of significantly higher optical rotation than a natural source. Similar synthetic strategies have been used to obtain several related compounds, including a decalin bearing an exocyclic olefin and a highly substituted cyclohexane, that can be viewed as hybrids of the trans-fused avarol and cis-fused arenarol skeletons.