Efficient Syntheses of the Polyene Fragments Present in Amphidinols

Cossy, Janine; Tsuchiya, Tomoki; Ferrié, Laurent; Reymond, Sébastien; Kreuzer, Thomas; Colobert, Françoise; Jourdain, Pierre; Markó, István E.

doi:10.1055/s-2007-984910

Cited by 23 publications

(7 citation statements)

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“…This compound was then converted to the C26-C42 fragment 106 in four steps involving a Claisen rearrangement 100 of a 1,5-diene to introduce the C30-C31 double bond (Scheme 34). 101,105,106,112,115,119,123,125 These three groups are working together on the synthesis of AM3. The rst strategy envisaged to construct AM3 was disclosed by Cossy and Bouzbouz and consisted of the construction of the C30-C31 and the C52-C53 bonds using olenations.…”

Section: Synthesis Of the C1-c25 Fragmentmentioning

confidence: 99%

“…104 Aer acetylation of the resulting homoallylic alcohol 111, a third cross-metathesis was realized with methyl acrylate to afford compound 112 (C1-C14 fragment) (Scheme 35). 105,106 This C53-C67 fragment corresponds to the skipped polyenic fragment. Two syntheses were realized, one by the Colobert's team 105 and the other one by Cossy et al 106 Colobert et al used their own know-how, a reduction/benzoylation/reductive elimination sequence to synthesize the polyene motif starting from bis-acetylenic precursors.…”

Section: Synthesis Of the C1-c14 Fragment (Cossy And Bouz-bouzmentioning

confidence: 99%

“…105,106 This C53-C67 fragment corresponds to the skipped polyenic fragment. Two syntheses were realized, one by the Colobert's team 105 and the other one by Cossy et al 106 Colobert et al used their own know-how, a reduction/benzoylation/reductive elimination sequence to synthesize the polyene motif starting from bis-acetylenic precursors. The synthesis of the C53-C67 fragment started with butadiyne 113.…”

Section: Synthesis Of the C1-c14 Fragment (Cossy And Bouz-bouzmentioning

confidence: 99%

“…The second synthesis of the C53-C67 fragment was achieved by Cossy et al, 106 starting from sorbic acid by employing a chemoselective dienamide cross-metathesis and a Julia-Kocienski olenation as the key steps. Sorbic acid was transformed to the dienic aldehyde 121 in three steps.…”

Section: Synthesis Of the C1-c14 Fragment (Cossy And Bouz-bouzmentioning

confidence: 99%

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Isolation, structural determination and synthetic approaches toward amphidinol 3

Bensoussan

Rival²,

Hanquet³

et al. 2014

Nat. Prod. Rep.

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Section: Synthesis Of the C1-c25 Fragmentmentioning

confidence: 99%

Section: Synthesis Of the C1-c14 Fragment (Cossy And Bouz-bouzmentioning

confidence: 99%

Section: Synthesis Of the C1-c14 Fragment (Cossy And Bouz-bouzmentioning

confidence: 99%

Section: Synthesis Of the C1-c14 Fragment (Cossy And Bouz-bouzmentioning

confidence: 99%

See 2 more Smart Citations

Isolation, structural determination and synthetic approaches toward amphidinol 3

Bensoussan

Rival²,

Hanquet³

et al. 2014

Nat. Prod. Rep.

Self Cite

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“…The chemoselective cross metathesis of a sorbic acid Weinreb's amide derivative with TBS-protected pent-1-en-5-ol in the presence of HG II catalyst was employed as a key step in the synthesis of the polyene fragment of amphidinols (Scheme 8) [34].…”

Section: Introductionmentioning

confidence: 99%

Application of Cross Metathesis in Diene and Polyene Synthesis

Wojtkielewicz

2013

COS

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Olefin metathesis has become a useful method in organic synthesis, rivaling palladium catalyzed C-C bond forming reactions as well as more traditional olefination processes. Olefin cross metathesis (CM) emerged later than ring closing metathesis and ring opening metathesis polymerization due to poor selectivity control. However, after the discovery of more active second generation catalysts and elaboration by Grubbs of an empirical model to predict the outcome of these reactions, cross metathesis has found wide application in the synthesis of various alkenes including those that are sterically demanding or highly functionalized. In recent years enyne cross metathesis and metathetic coupling between alkene and diene or polyene were widely tested as alternative, convenient methods of diene and polyene preparation. In this review the application of ene-diene CM, ene-polyene CM, diene-polyene CM, ene-yne CM and alkene CM combined with other reactions in the synthesis of conjugated dienes and polyenes is presented. The aim of this article is to demonstrate not only the scope of CM application in the synthesis of conjugated dienes and polyenes but also its limitations associated mainly with problems of regio-and stereoselectivity control and how the encountered difficulties led to a better understanding of these processes and the discovery of more effective reaction conditions.

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TheJulia–Kocienski Olefination

Blakemore¹,

Sephton

Ciganek

2018

Organic Reactions

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The Julia–Kocienski olefination is a direct connective synthesis of alkenes via the addition of metalated aryl alkyl sulfones to carbonyl compounds. The activating aromatic group associated with the sulfone must possess electrophilic character, and alkene formation occurs via β‐alkoxy sulfone formation, transfer of the aryl group from sulfur to oxygen via a Smiles rearrangement, and then elimination of sulfur dioxide and an aryloxide anion from the resulting β‐aryloxy sulfinate anion. The olefination process itself and the methods used to prepare the requisite sulfone substrates are tolerant of a wide variety of functional groups, and a variety of alkene targets can be prepared. Stereoselectivity is dependent on the nature of the sulfone, the carbonyl compound, the activating aryl moiety, and the reaction conditions. This chapter describes theoretical and operational aspects of the Julia–Kocienski olefination such that the reader will be able to obtain optimal results in his/her own research. A detailed mechanistic overview is included to account for the factors that influence stereoselectivity and yield. Methods for introducing sulfone activators into fragments of interest, best practices for generating sulfone anions, and optimal strategies for targeting different classes of alkene targets are discussed. Functional group compatibilities, reaction variants, and a comparison to other methods of alkene synthesis are also presented. Tabular surveys are organized according to type of alkene synthesized, with an emphasis on the degree of substitution and the level of conjugation about the newly formed double bond. The literature is covered from the initial disclosure of the Julia–Kocienski olefination in 1991 to the first quarter of 2016.

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Efficient Syntheses of the Polyene Fragments Present in Amphidinols

Abstract: The C53-C67 and C53-C65 polyene fragments of amphidinols have been synthesized in an efficient and convergent fashion from sorbic acid in good overall yields (30-31%) by employing a chemoselective cross-metathesis of a Weinreb amide and a Julia-Kocienski olefination as the key steps.

Cited by 23 publications

References 9 publications

Isolation, structural determination and synthetic approaches toward amphidinol 3

Isolation, structural determination and synthetic approaches toward amphidinol 3

Application of Cross Metathesis in Diene and Polyene Synthesis

TheJulia–Kocienski Olefination

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