Total Synthesis, Stereochemical Reassignment, and Biological Evaluation of (−)‐Lyngbyaloside B

Fuwa, Haruhiko; Okuaki, Yuta; Yamagata, Naoya; Sasaki, Makoto

doi:10.1002/ange.201409629

Cited by 14 publications

(2 citation statements)

References 76 publications

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“…Similar strategies targeting the central macrolide were reported by Arseniyadis (ElMarrouni et al 2011), Fuwa (Fuwa et al, 2015), and Taylor (Chang et al, 2015) (Scheme 4). Arseniyadis successfully used C-C bond formation via olefin metathesis with key intermediates 34 and 35; 36 was obtained by heating the dioxinone intermediate.…”

Section: Macrocyclic Natural Product Synthesissupporting

confidence: 63%

Recent applications of dioxinone derivatives for macrocyclic natural product and terpenoid synthesis

2022

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Dioxinone derivatives, a class of acetoacetate derivatives, have attracted widespread attention because of their multiple reactive sites, high reactivity, unique chemical properties, and potential synthetic applications. The dioxinone group is also stable under a wide range of reaction conditions, including strong acids, as well as a variety of transition-metal-catalysed processes, such as olefin metathesis and Pd-mediated cross-coupling. The inherent reactivity and diverse applications of dioxinones make them valuable reactive intermediates in organic synthesis. The conversion of dioxinones to acylketenes and their subsequent nucleophilic capture is also an excellent strategy for synthesising β-keto acid derivatives, which can be applied even in complex molecular synthesis. This review focuses on the recent advances in the application of dioxinones in synthetic method research and the total synthesis of natural products, highlighting the exceptional utility of these synthetic methodologies in the construction of macrocyclic cores and terpenoid skeletons. In particular, successful transformations of dioxinone fragments are discussed.

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Section: Macrocyclic Natural Product Synthesissupporting

confidence: 63%

Recent applications of dioxinone derivatives for macrocyclic natural product and terpenoid synthesis

2022

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“… 361 Here, the corresponding vinylogous Felkin-adduct (5,6- syn )- 523 was obtained in a very good 90% yield as a single isomer. Similarly, Yadav et al (2012) 362 and Fuwa et al (2015, 2016) 363 , 364 applied the methodology with comparable results in the synthesis of either the C1–C14 macrolactone core of (−)-callipeltoside A ( Scheme 140 , entry 2), or the cytotoxic14-membered macrolide (−)-lyngbyaloside B (entry 3). A favorable 1,3-induced diastereoselective VMAR was studied by Forsyth’s group in the effort to synthesize the natural product phorboxazole A (entry 4).…”

Section: Vinylogous Esters and Lactonesmentioning

confidence: 95%

New Developments of the Principle of Vinylogy as Applied to π-Extended Enolate-Type Donor Systems

et al. 2020

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The principle of vinylogy states that the electronic effects of a functional group in a molecule are possibly transmitted to a distal position through interposed conjugated multiple bonds. As an emblematic case, the nucleophilic character of a π-extended enolate-type chain system may be relayed from the legitimate α-site to the vinylogous γ, ε, ..., ω remote carbon sites along the chain, provided that suitable HOMO-raising strategies are adopted to transform the unsaturated pronucleophilic precursors into the reactive polyenolate species. On the other hand, when “unnatural” carbonyl ipso -sites are activated as nucleophiles (umpolung), vinylogation extends the nucleophilic character to “unnatural” β, δ, ... remote sites. Merging the principle of vinylogy with activation modalities and concepts such as iminium ion/enamine organocatalysis, NHC-organocatalysis, cooperative organo/metal catalysis, bifunctional organocatalysis, dicyanoalkylidene activation, and organocascade reactions represents an impressive step forward for all vinylogous transformations. This review article celebrates this evolutionary progress, by collecting, comparing, and critically describing the achievements made over the nine year period 2010–2018, in the generation of vinylogous enolate-type donor substrates and their use in chemical synthesis.

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Total Synthesis and Stereochemical Revision of Iriomoteolide‐2a

Sakamoto¹

2018

Angewandte Chemie

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Total syntheses of the proposed and correct structures of iriomoteolide‐2a, a cytotoxic marine macrolide natural product with an unusual 23‐membered macrolactone skeleton, have been accomplished for the first time. The synthesis of the correct structure involves an asymmetric epoxidation/diepoxide cyclization cascade for the construction of the bis(tetrahydrofuran) moiety, a Suzuki–Miyaura coupling for the fragment assembly, and a ring‐closing metathesis for the closure of the macrocyclic backbone. In addition, the original stereochemical assignment of iriomoteolide‐2a was revised.

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Total Synthesis, Stereochemical Reassignment, and Biological Evaluation of (−)‐Lyngbyaloside B

Cited by 14 publications

References 76 publications

Recent applications of dioxinone derivatives for macrocyclic natural product and terpenoid synthesis

Recent applications of dioxinone derivatives for macrocyclic natural product and terpenoid synthesis

New Developments of the Principle of Vinylogy as Applied to π-Extended Enolate-Type Donor Systems

Total Synthesis and Stereochemical Revision of Iriomoteolide‐2a

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