Total Synthesis and Structural Reassignment of Lyngbyaloside C Highlighted by Intermolecular Ketene Esterification

Chang, Chia‐Fu; Stefan, Eric; Taylor, Richard E.

doi:10.1002/chem.201502132

Cited by 22 publications

(12 citation statements)

References 67 publications

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“…The correct structure 86 of (−)‐lyngbyaloside B was finally verified in an unambiguous manner through total synthesis. In line with our conclusion, Taylor and co‐workers very recently reported the total synthesis of (−)‐18 Z ‐lyngbyaloside C and revised the original stereochemical assignment of the proposed structure 4 at the same positions as 1 (C‐10, C‐11, and C‐13) . Therefore, we suggest that the originally assigned structure 2 of lyngbouilloside should also be reconsidered carefully.…”

Section: Resultssupporting

confidence: 87%

Total Synthesis and Complete Stereostructure of a Marine Macrolide Glycoside, (−)‐Lyngbyaloside B

Fuwa

Yamagata

Okuaki

et al. 2016

Chemistry A European J

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We have described in detail the total synthesis of both the proposed and correct structures of (-)-lyngbyaloside B, which facilitated the elucidation of the complete stereostructure of this natural product. Our study began with the total synthesis of 13-demethyllyngbyaloside B, in which an esterification/ring-closing metathesis (RCM) strategy was successfully used for the efficient construction of the macrocycle. We also established reliable methods for the introduction of the conjugated diene side chain and the l-rhamnose residue onto the macrocyclic framework. However, the esterification/RCM strategy proved ineffective for the parent natural product because of the difficulties in acylating the sterically encumbered C-13 tertiary alcohol; macrolactionization of a seco-acid was also extensively investigated under various conditions without success. We finally completed the total synthesis of the proposed structure of (-)-lyngbyaloside B by means of a macrolactonization that involves an acyl ketene as the reactive species. However, the NMR spectroscopic data of our synthetic material did not match those of the authentic material, which indicated that the proposed structure must be re-examined. Inspection of the NMR spectroscopic data of the natural product and molecular mechanics calculations led us to postulate that the configuration of the C-10, C-11, and C-13 stereogenic centers had been incorrectly assigned in the proposed structure. Finally, our revised structure of (-)-lyngbyaloside B was unambiguously verified through total synthesis.

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Section: Resultssupporting

confidence: 87%

Total Synthesis and Complete Stereostructure of a Marine Macrolide Glycoside, (−)‐Lyngbyaloside B

Fuwa

Yamagata

Okuaki

et al. 2016

Chemistry A European J

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“…Compounds 2-5 were identified by comparison of HRESIMS, 1 H NMR, and COSY spectral data to the literature [17][18][19][20] (data provided in supplementary material). Total syntheses have been reported for 2-4, confirming the structures of 2 [22] and 3 [23] while leading to the structural revision of three stereogenic centers (C-10, 11, and 13) of 4 [24]. Two natural products that appeared to belong to the lyngbyabellin class of natural products, referred to as lyngbyabellin-like 1 (LYN1) and 2 (LYN2), were isolated in very low yields (2.2 and 2.8 µg, respectively) which hindered full structure elucidation.…”

Section: Molecular Structures Of Natural Products From Moorea Producenssupporting

confidence: 52%

Antimalarial Peptide and Polyketide Natural Products from the Fijian Marine Cyanobacterium Moorea producens

et al. 2020

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A new cyclic peptide, kakeromamide B (1), and previously described cytotoxic cyanobacterial natural products ulongamide A (2), lyngbyabellin A (3), 18E-lyngbyaloside C (4), and lyngbyaloside (5) were identified from an antimalarial extract of the Fijian marine cyanobacterium Moorea producens. Compound 1 exhibited moderate activity against Plasmodium falciparum blood-stages with an EC50 value of 8.9 µM whereas 2 and 3 were more potent with EC50 values of 0.99 µM and 1.5 nM, respectively. Compounds 1, 4, and 5 displayed moderate liver-stage antimalarial activity against P. berghei liver schizonts with EC50 values of 11, 7.1, and 4.5 µM, respectively. The threading-based computational method FINDSITEcomb2.0 predicted the binding of 1 and 2 to potentially druggable proteins of Plasmodium falciparum, prompting formulation of hypotheses about possible mechanisms of action. Kakeromamide B (1) was predicted to bind to several Plasmodium actin-like proteins and a sortilin protein suggesting possible interference with parasite invasion of host cells. When 1 was tested in a mammalian actin polymerization assay, it stimulated actin polymerization in a dose-dependent manner, suggesting that 1 does, in fact, interact with actin.

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“…Total syntheses of the proposed 456 and correct structures (709) of (À)-lyngbyaloside B were completed 457 and total synthesis of the (18Z) and (18E) isomers of lyngbyaloside C 458 resulted in reassignment of the structures to 710 and 711 respectively. 459 As a result, it was suggested that the structure of lyngbouilloside 460 should likely also be reconsidered. 459 Total syntheses of the acyclic depsipeptide maedamide 461 and cyclodepsipeptide largamide B 462 also resulted in stereochemical revision of their structures to 712 (ref.…”

Section: Cyanobacteriamentioning

confidence: 99%

“…459 As a result, it was suggested that the structure of lyngbouilloside 460 should likely also be reconsidered. 459 Total syntheses of the acyclic depsipeptide maedamide 461 and cyclodepsipeptide largamide B 462 also resulted in stereochemical revision of their structures to 712 (ref. 463) and 713 (ref.…”

Section: Cyanobacteriamentioning

confidence: 99%

Marine natural products

et al. 2017

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Covering: 2015. Previous review: Nat. Prod. Rep., 2016, 33, 382-431This review covers the literature published in 2015 for marine natural products (MNPs), with 1220 citations (792 for the period January to December 2015) referring to compounds isolated from marine microorganisms and phytoplankton, green, brown and red algae, sponges, cnidarians, bryozoans, molluscs, tunicates, echinoderms, mangroves and other intertidal plants and microorganisms. The emphasis is on new compounds (1340 in 429 papers for 2015), together with the relevant biological activities, source organisms and country of origin. Reviews, biosynthetic studies, first syntheses, and syntheses that lead to the revision of structures or stereochemistries, have been included.

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Total Synthesis and Structural Reassignment of Lyngbyaloside C Highlighted by Intermolecular Ketene Esterification

Cited by 22 publications

References 67 publications

Total Synthesis and Complete Stereostructure of a Marine Macrolide Glycoside, (−)‐Lyngbyaloside B

Total Synthesis and Complete Stereostructure of a Marine Macrolide Glycoside, (−)‐Lyngbyaloside B

Antimalarial Peptide and Polyketide Natural Products from the Fijian Marine Cyanobacterium Moorea producens

Marine natural products

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