Synthesis of a Highly Functionalized Triquinane: Studies Towards a Total Synthesis of Subergorgic Acid and Its Analogues

Dragojlović, Veljko

doi:10.3390/50400674

Cited by 9 publications

(3 citation statements)

References 53 publications

(124 reference statements)

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“…The enone 11 , which could serve as a key intermediate for the synthesis of a variety of centro -substituted triquinacene derivatives, was then prepared in high yield on oxidation of the corresponding trimethylsilyl enol ether of the monoacetal 10 with palladium(II) acetate . Unfortunately, the yield of this process on employment of a substoichiometric amount of palladium(II) acetate with benzoquinone or dichlorodicyanoquinone as a co-oxidant proved to be less than satisfactory .…”

mentioning

confidence: 99%

Versatile Route to centro-Substituted Triquinacene Derivatives: Synthesis of 10-Phenyltriquinacene

2003

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[reaction: see text] A versatile route to prepare centro-substituted triquinacene derivatives (1, R = various substituents), as exemplified by the preparation of 10-phenyltriquinacene (1, R = Ph), is reported. The quaternary, centro substituent (C-10) was installed by a trimethylsilyl chloride-promoted conjugate addition reaction of an organocuprate, derived from phenylmagnesium bromide, and the protected bicyclic enone (11). The resultant trimethylsilyl enol ether was then converted regioselectively to the C-2-allylated conjugate addition products (13, R = Ph). The allyl moiety, following oxidative cleavage of the carbon-carbon double bond, was used to elaborate the tricyclic ring system by an intramolecular aldol/acetal deprotection reaction. The product of this reaction was then converted to the target compound using a standard series of functional group transformation reactions.

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mentioning

confidence: 99%

Versatile Route to centro-Substituted Triquinacene Derivatives: Synthesis of 10-Phenyltriquinacene

2003

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“…175 Studies towards a total synthesis of subergonic acid have been carried out. 176 13 Humulane, pentalenane, hirsutane, sterpurane, protoilludane, illudane, illudalane, africanane and asteriscane Some chemical transformations of zerumbone have been described. This humulene derivative had been isolated from Zingiber zerumbet.…”

Section: Himachalane Longifolane and Longipinanementioning

confidence: 99%

Untitled

2001

Nat. Prod. Rep.

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“…Subergorgic acid is another interesting triquinane natural product isolated by Fenical et al from the Pacific gorgonian coral Subergorgia suberosa and it shows high cardiotoxic activity, anti “Soman” toxicity, and anticholinesterase activity . Because of the wide variety of biological activities, the Iwata, Wender, Crimmins, Paquette, Dragojlovic groups actively engaged in the synthesis of subergorgic acid and its analogues. Other natural products like pentalenene, silphinene, silphiperfol-6-ene, isocomene, arnicenone, and cantabrenonic acid also show useful biological activities such as antibiotic, antitumor, antimicrobial, cardiotoxic activity …”

Section: Introductionmentioning

confidence: 99%

A Modular Approach to Angularly Fused Polyquinanes via Ring-Rearrangement Metathesis: Synthetic Access to Cameroonanol Analogues and the Basic Core of Subergorgic Acid and Crinipellin

Kotha

Keesari

2021

J. Org. Chem.

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We describe a modular approach to angularly fused polyquinanes that are core units of many natural products such as cameroonanol, subergorgic acid, and crinepellin, etc. in excellent yields by employing atom-economic ring-rearrangement metathesis as a key step. Our work highlights, the synthesis of cameroonanol analogues 1–6 and their ester derivatives by using the stereoselective reduction of the carbonyl group by using DIBAL-H- and DCC-mediated coupling as the key reactions. The subergorgic acid core 7 was produced by LDA-mediated kinetically controlled regio- and stereoselective ring-junction allylation as a critical step. Moreover, it is worth mentioning that the present strategy relies on a less explored exo-dicyclopentadiene-1-one (8) and produces highly congested polycyclic frameworks containing up to seven contiguous stereogenic centers including quaternary carbons up to two. All of the new molecules were characterized by NMR data. The structure and relative stereochemistry of some compounds were confirmed by chemical methods and further supported by single-crystal X-ray diffraction studies. The newly reported tri- and tetraquinane skeletons are present in many naturally occurring bioactive polyquinanes. Hence, this strategy is useful for designing various “druglike molecules” and expands the chemical space of cyclopentanoids that are useful in medicinal chemistry.

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Synthesis of a Highly Functionalized Triquinane: Studies Towards a Total Synthesis of Subergorgic Acid and Its Analogues

Cited by 9 publications

References 53 publications

Versatile Route to centro-Substituted Triquinacene Derivatives: Synthesis of 10-Phenyltriquinacene

Versatile Route to centro-Substituted Triquinacene Derivatives: Synthesis of 10-Phenyltriquinacene

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A Modular Approach to Angularly Fused Polyquinanes via Ring-Rearrangement Metathesis: Synthetic Access to Cameroonanol Analogues and the Basic Core of Subergorgic Acid and Crinipellin

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