Total Synthesis of Amphidinolide F

Valot, Gaëlle; Regens, Christopher S.; O’Malley, Daniel P.; Godineau, Edouard; Takikawa, Hiroshi; Fürstner, Alois

doi:10.1002/anie.201301700

Cited by 124 publications

(46 citation statements)

References 88 publications

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“…[59,65] The ease with which 61 was formed by this catalyst is remarkable if one considers that this particular compound is unstable even when stored in the refrigerator; it eventually undergoes an irreversible straindriven ring expansion via two consecutive [3,3]-rearrangements of the pentadienyl ester subunit with formation of lactone 62, the structure of which has been unambiguously assigned. The inherent chemical instability of 61 expressed in this behavior is also thought to be the major reason why the final sequence of ruthenium catalyzed trans-hydrosilylation followed by protodesilylation and selective cleavage of the TES ether off the C8-OH group was challenging.…”

Section: Formation Of Non-terminal Alkynes By Reductive Alkylationmentioning

confidence: 98%

A New Method for the Preparation of Non‐Terminal Alkynes: Application to the Total Syntheses of Tulearin A and C

Lehr

Schulthoff

Ueda

et al. 2014

Chemistry A European J

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Lactones are known to react with the reagent generated in situ from CCl4 and PPh3 in a Wittig-type fashion to give gem-dichloro-olefin derivatives. Such compounds are now shown to undergo reductive alkylation on treatment with organolithium reagents RLi to furnish acetylene derivatives bearing the substituent R at their termini (R=Me, n-, sec-, tert-alkyl, silyl); the reaction can be catalyzed with either Cu(acac)2 or Fe(acac)3 /1,2-diaminobenzene. Two alkynol derivatives prepared in this way from readily accessible lactone precursors served as the key building blocks for the total syntheses of the cytotoxic marine macrolides tulearin A (1) and C (2). The assembly of these fragile targets hinged upon ring closing alkyne metathesis (RCAM) followed by a formal trans-reduction of the resulting cycloalkynes via trans-hydrosilylation/protodesilylation.

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Section: Formation Of Non-terminal Alkynes By Reductive Alkylationmentioning

confidence: 98%

A New Method for the Preparation of Non‐Terminal Alkynes: Application to the Total Syntheses of Tulearin A and C

Lehr

Schulthoff

Ueda

et al. 2014

Chemistry A European J

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“…Another nice example of the many options offered for the preparation of THF was presented by Fürstner and co-workers for the synthesis of Amphidinolide C and F. 99,100 Actually, the authors used a TBAF-mediated hydroalkoxylation for the synthesis of the fragment C16-C24, and for the synthesis of C1-C9 fragment, a cobalt catalyzed oxidative cyclization using (Co(nmp) 2 ) catalyst (Scheme 36). Finally, the same catalytic system was employed by the team of Dias for the synthesis of (˗)-Goniotrionin.…”

Section: A C C E P T E D Accepted Manuscriptmentioning

confidence: 98%

Recent advances in the synthesis of tetrahydrofurans and applications in total synthesis

et al. 2016

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Mousseron. His research interests include the total synthesis of oxygenated cyclic and non cyclic metabolites of polyunsaturated fatty acids, mainly leukotrienes, iso-, phyto-and neuroprostanes, as well as dihydroxylated PUFAs and more recently lipophenols and the understanding of the role of such bioactive lipids and lipophenols by developing collaborations with chemists, biochemists, biologists and clinicians across the world. Jean-Marie Galano studied chemistry at Paul Cézanne Université Marseille and obtained his PhD under the supervision of Honoré Monti in 2001. He then moved to the University of Oxford to pursue a postdoctoral fellowship with David H. Hodgson on the development of new methods for the total synthesis of natural products. In October 2005 he joined the CNRS as a Chargé de Recherche at Université of Montpellier. His research focuses on the total synthesis and discovery of new lipid metabolites, and to discover their potential implications in human health. AbstractMany natural products contain tetrahydrofuran (THF) moieties. Those molecules, often biologically active, may be structurally diverse, e.g. cis or trans THF, mono-, di-, tri-or tetrasubstituted on the furan ring. Thus, the construction of THF is of great interest for the community of organic chemists; especially in developing new methodologies, and applying them in the total synthesis of natural products. The aim of this review is to report recent advances in the field of THF synthesis, as well as the application of these methods to the synthesis of bioactive compounds.

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“…In 2013, the Fürstner group published a successful approach to amphidinolide F ( 24 ) applying an oxidative type C Mukaiyama cyclization reaction for the THF segment 22 (Scheme 7) [69–70]. Therefore, enantiomerically pure epoxide 20 was converted to 5-hydroxyalkene 21 , the oxidative cyclization precursor in this total synthesis.…”

Section: Reviewmentioning

confidence: 99%

“…Therefore, enantiomerically pure epoxide 20 was converted to 5-hydroxyalkene 21 , the oxidative cyclization precursor in this total synthesis. The subsequent cobalt-catalyzed cyclization reaction proceeded chemoselectively in the presence of the alkyne moiety and provided the trans -disubstituted THF 22 in high yield [69–71]. Finally, building block 23 , one important fragment in the total synthesis of amphidinolide F ( 24 ), was accessible in good overall yield and high diastereoselectivity (dr ≈ 95:5) in only four steps (Scheme 7).…”

Section: Reviewmentioning

confidence: 99%

The direct oxidative diene cyclization and related reactions in natural product synthesis

Adrian¹,

Gross²,

Stark³

2016

Beilstein J. Org. Chem.

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SummaryThe direct oxidative cyclization of 1,5-dienes is a valuable synthetic method for the (dia)stereoselective preparation of substituted tetrahydrofurans. Closely related reactions start from 5,6-dihydroxy or 5-hydroxyalkenes to generate similar products in a mechanistically analogous manner. After a brief overview on the history of this group of transformations and a survey on mechanistic and stereochemical aspects, this review article provides a summary on applications in natural product synthesis. Moreover, current limitations and future directions in this area of chemistry are discussed.

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Total Synthesis of Amphidinolide F

Cited by 124 publications

References 88 publications

A New Method for the Preparation of Non‐Terminal Alkynes: Application to the Total Syntheses of Tulearin A and C

A New Method for the Preparation of Non‐Terminal Alkynes: Application to the Total Syntheses of Tulearin A and C

Recent advances in the synthesis of tetrahydrofurans and applications in total synthesis

The direct oxidative diene cyclization and related reactions in natural product synthesis

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