Total Synthesis of Natural Myriaporones

Pérez, Marta; Pozo, Carlos del; Reyes, Fernando; Rodríguez, Alberto; Francesch, Andrés; Echavarren, Antonio M.; Cuevas, Carmen

doi:10.1002/anie.200353313

Cited by 39 publications

(8 citation statements)

References 24 publications

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“…577,578 The total syntheses of myriaporones 1 648, 3 649 and 4 650 have been reported by two groups allowing determination of the previously undetermined C-5 and C-6 configurations. 579,580 The first enantioselective synthesis of the Flustra foliacea metabolite (-)-flustramine B 581 has been accomplished, employing a cascade addition-cyclisation strategy. 582…”

Section: Bryozoansmentioning

confidence: 99%

Marine natural products

et al. 2006

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This review covers the literature published in 2004 for marine natural products, with 693 citations (491 for the period January to December 2004) referring to compounds isolated from marine microorganisms and phytoplankton, green algae, brown algae, red algae, sponges, coelenterates, bryozoans, molluscs, tunicates and echinoderms. The emphasis is on new compounds (716 for 2004), together with their relevant biological activities, source organisms and country of origin. Biosynthetic studies (8), and syntheses (80), including those that lead to the revision of structures or stereochemistries, have been included.

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Section: Bryozoansmentioning

confidence: 99%

Marine natural products

et al. 2006

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“…6 In subsequent synthetic studies of the myriaporones, equilibrium mixtures were also reported. 7,8 Therefore, structure determination of the two isomers was carried out on the mixture of 1 and 2 . HRESIMS data ( m/z 665.3146 [M + Na] + , Δ = 0.3 ppm) indicated that the molecular formula for both 1 and 2 , was C 32 H 50 O 13 ; two oxygens more than the molecular formula for tedanolide ( 5 ), and 42 Da less than the molecular weight of candidaspongiolide A ( 3 ).…”

mentioning

confidence: 99%

New Candidaspongiolides, Tedanolide Analogues That Selectively Inhibit Melanoma Cell Growth

Whitson¹,

Pluchino²,

Hall³

et al. 2011

Org. Lett.

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Extracts of the sponge genus Candidaspongia showed selective cytotoxicity towards melanoma cells in the NCI 60-cell-line screen. Continued investigation of the Candidaspongia sp. extracts led to the isolation of three new tedanolide analogs, precandidaspongiolides A (1) and B (2), and candidaspongiolide B (4), as well as candidaspongiolide A (3) and tedanolide (5). Semi-synthetic derivatives were also generated to develop SAR. Candidaspongiolides A/B were the most potent and showed low nanomolar activity against several melanoma cell lines.

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“…An important phase of this research has been completed. The efficiency of the synthetic route presented herein has enabled the preparation of significant quantities of these interesting marine natural products as well as analogues 12. Studies currently underway will seek to identify the biological receptor and mode of action of the myriaporones.…”

Section: Methodsmentioning

confidence: 99%

Total Synthesis and Stereochemical Assignment of Myriaporones 1, 3, and 4

Fleming

Taylor

2004

Angew Chem Int Ed

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The natural products tedanolide (1 a) and 13-deoxytedanolide (1 b), which were isolated by Schmitz et al. [1] and Fusetani et al., [2] respectively, exhibit picomolar activity against a range of cancer cell lines. Their biological activity coupled with their scarcity has prompted considerable synthetic attention.[3] Our interest in these compounds stems from the isolation of a related class of natural products, the myriaporones (2 a-d), reported by Rinehart et al. in 1995. [4, 5] The myriaporones are nearly identical structurally to the C10-C23 portion of tedanolide (1 a); it is therefore possible that these two classes of compounds share the same biological receptor and have similar modes of action. As a result of their limited availability, the biology of both classes remains a mystery. Therefore, our goal is to provide material to facilitate such studies and, herein, we report the total synthesis of myriaporones 1, 3, and 4 (2 a, c, d) and the unambiguous assignment of their previously undetermined stereogenic configurations at C5 and C6.Recently, we reported the completion of the carbon skeleton of myriaporone 1 (2 a) through a stereoselective homoallenylboration and a nitrile oxide cycloaddition.[5a]Construction of myriaporone 4 (2 d) began with known alcohol 3[3c] (Scheme 1). Oxidation with IBX [6] was followed by an Evans aldol [7] reaction to set the C8 and C9 stereocenters in high yield and excellent diastereoselectivity. During the course of that work, incorporation of the epoxide at an early stage limited the scope of reaction conditions that subsequent intermediates could withstand and ultimately prevented completion of the total synthesis. Since then, Loh and Feng [3g] and Smith III et al. [3k] reported highly selective late-stage epoxidations in their efforts toward tedanolide. With these results as precedence, our focus switched to the incorporation of this particularly sensitive functional group in the penultimate step of the synthesis. Scheme 1. Synthesis of C5-epimeric isoxazolines 9 a and 9 b. Reagents and conditions: a) IBX, 95 %; b) Bu 2 BOTf, Et 3 N, 93 %; c) TBSOTf, 85 %; d) LiBH 4 ; e) TBSCl, 89 % (two steps); f) OsO 4 , NMO, 95 %; g) NaIO 4 , 84%; h) Bu 2 BOTf, Et 3 N, 99 %; i) LiBH 4 ; j) TBSCl, 92 % (two steps); k) PrNO 2 , PhNCO, 64 %; l) DDQ, 88 %; m) IBX; n) Ph 3 P= CHCH 3 , 63 % (two steps). IBX = o-iodoxybenzoic acid; Tf = trifluoromethanesulfonyl; TBS = tert-butyldimethylsilyl; NMO = N-methylmorpholine-N-oxide; DDQ = 2,3-dichloro-5,6-dicyano-1,4-benzoquinone.

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Total Synthesis of Natural Myriaporones

Cited by 39 publications

References 24 publications

Marine natural products

Marine natural products

New Candidaspongiolides, Tedanolide Analogues That Selectively Inhibit Melanoma Cell Growth

Total Synthesis and Stereochemical Assignment of Myriaporones 1, 3, and 4

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