First Enantioselective Total Synthesis and Structure Determination of the Anthrapyran Metabolite γ-Indomycinone

Tietze, Lutz F.; Singidi, Ramakrishna Reddy; Gericke, Kersten M.

doi:10.1021/ol062492b

Cited by 32 publications

(23 citation statements)

References 36 publications

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“…In the first step the aerobic oxidation of 1,5-dihydroxynaphthalene (28) using substoichiometric amounts of freshly recrystallized copper(I) chloride to furnish juglone (29) was achieved in yields according to those reported in the literature. [43] Dichlorination of 29 and subsequent thermal elimination of HCl afforded chlorojuglone 30 [44] and its regioisomer as a mixture, the separation of which could not be accomplished by column chromatography.…”

Section: Introductionmentioning

confidence: 99%

Total Synthesis of cyclo‐Mumbaistatin Analogues through Anionic Homo‐Fries Rearrangement

Neufeind

Hülsken

Neudörfl

et al. 2011

Chemistry A European J

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The structurally unique polyketide mumbaistatin is the strongest naturally occurring inhibitor of glucose-6-phosphate translocase-1 (G6P-T1), which is a promising target for drugs against type-2 diabetes mellitus and angiogenic processes associated with brain tumor development. Despite its high relevance, mumbaistatin has so far withstood all attempts towards its total synthesis. In the present study an efficient total synthesis of a deoxy-mumbaistatin analogue containing the complete carbon skeleton and a spirolactone motif closely resembling the natural product in its cyclized form was elaborated. Key steps of the synthesis are a Diels-Alder cycloaddition for the construction of the fully functionalized anthraquinone moiety and an anionic homo-Fries rearrangement to build up the tetra-ortho-substituted benzophenone core motif, from which a spiroketal lactone forms in a spontaneous process. The elaborated strategy opens an entry to a variety of new analogs of mumbaistatin and cyclo-mumbaistatin and may be exploited for the total synthesis of the natural product itself in the future.

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Section: Introductionmentioning

confidence: 99%

Total Synthesis of cyclo‐Mumbaistatin Analogues through Anionic Homo‐Fries Rearrangement

Neufeind

Hülsken

Neudörfl

et al. 2011

Chemistry A European J

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“…The absolute configuration of the stereocentre at C-14 was determined on the basis of comparison of CD data to metabolites 1 and 2 , and optical rotation values to both the synthetic and natural anthraquinone-pyran metabolite, γ-indomycinone. [8] As described earlier, compound 6 displays Cotton effects nearly opposite to those of 1 and 2 . In addition, 6 ([α] D −49, c 0.10, dimethyl sulfoxide (DMSO)) afforded a net negative rotation, which coincided with the sign of the natural product ([α] D −5.5, c 0.11, DMSO, 14 S ) and was opposite to that of the synthetic analogue ([α] D +4.0, c 0.10, DMSO, 14 R ).…”

Section: Resultsmentioning

confidence: 74%

Saliniquinones A - F, New Members of the Highly Cytotoxic Anthraquinone-γ-Pyrones from the Marine Actinomycete Salinispora arenicola

et al. 2010

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Six new anthraquinone-γ-pyrones, saliniquinones A–F (1–6), which are related to metabolites of the pluramycin/altromycin class, were isolated from a fermentation broth of the marine actinomycete Salinispora arenicola (strain CNS-325). Their structures were determined by analysis of one- and two-dimensional NMR spectroscopic and high-resolution mass spectrometric data. The relative and absolute configurations of compounds 1–6 were determined by analysis of NOESY NMR spectroscopic data and by comparison of circular dichroism and optical rotation data with model compounds found in the literature. Saliniquinone A (1) exhibited potent inhibition of the human colon adenocarcinoma cell line (HCT-116) with an IC50 of 9.9 × 10−9 M. In the context of the biosynthetic diversity of S. arenicola, compounds 1–6 represent secondary metabolites that appear to be strain specific and thus occur outside of the core group of compounds commonly observed from this species.

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“…8 Several groups have developed syntheses of anthrapyranones, most commonly through various approaches to the 4-pyranone ring system D ring. These key reactions include; the BakerVenkataraman rearrangement with cyclisation, 9,10 a 6-endo-dig cyclisation of alkyne ketones, [11][12][13][14][15] a Friedel-Crafts acylation 16 and cyclisation of b-diketones 17,18 among others. 19,20 In 2013, we described a racemic synthesis of anthrapyranones through the annulation of a b-keto-sulfoxide and an aldehyde.…”

Section: Introductionmentioning

confidence: 99%

The synthesis and biological activity of novel anthracenone-pyranones and anthracenone-furans

Rixson

Abraham

Egoshi

et al. 2015

Bioorganic & Medicinal Chemistry

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First Enantioselective Total Synthesis and Structure Determination of the Anthrapyran Metabolite γ-Indomycinone

Abstract: The first total synthesis of (R)-gamma-indomycinone has been achieved which allowed the determination of the configuration of the stereogenic center of natural gamma-indomycinone as (S). The approach stands out for its generality and efficiency. [reaction: see text]

Cited by 32 publications

References 36 publications

Total Synthesis of cyclo‐Mumbaistatin Analogues through Anionic Homo‐Fries Rearrangement

Total Synthesis of cyclo‐Mumbaistatin Analogues through Anionic Homo‐Fries Rearrangement

Saliniquinones A - F, New Members of the Highly Cytotoxic Anthraquinone-γ-Pyrones from the Marine Actinomycete Salinispora arenicola

The synthesis and biological activity of novel anthracenone-pyranones and anthracenone-furans

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