Toward the Synthesis of (+)-Peloruside A via an Intramolecular Vinylogous Aldol Reaction

Gazaille, Jeffrey A.; Abramite, J. A.; Sammakia, Tarek

doi:10.1021/ol202966m

Cited by 31 publications

(12 citation statements)

References 35 publications

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“…An intramolecular version of the Yamamoto VAR was exploited by Sammakia and co-workers in 2012 for the preparation of an advanced intermediate for the synthesis of (+)-peloruside A, a polyoxygenated 16-membered macrolide with potent antimicotic activity ( Scheme 114 ). 299 The reaction was applied to open intermediate 416 bearing pronucleophilic crotonate and nonenolizable furfural moieties that were cyclized using ATPH ( M3 , 2.2 equiv) and LTMP (2.0 equiv) in toluene/THF at −78 °C. The corresponding 16-membered macrolactone 417 was accessed in 86% yield as a 6:1 diastereomeric mixture.…”

Section: Vinylogous Esters and Lactonesmentioning

confidence: 99%

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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Section: Vinylogous Esters and Lactonesmentioning

confidence: 99%

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

et al. 2020

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“…In addition, a chiral center is introduced through the Achmatowicz reaction, therefore many asymmetric variants could be developed subsequently, paving the routes to synthesize diastereoselective and optically active compounds 20 . Figure 1a presents a few representative biologically active products whose syntheses are benefited from the Achmatowicz reaction 21 – 23 . The Achmatowicz rearrangement was first reported in 1970s, utilizing Br 2 as the oxidant and methanol as the solvent to produce stable methoxylated furfuryl alcohol (Fig.…”

Section: Introductionmentioning

confidence: 99%

Electrocatalytic synthesis of heterocycles from biomass-derived furfuryl alcohols

Han

et al. 2021

Nat Commun

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It is very attractive yet underexplored to synthesize heterocyclic moieties pertaining to biologically active molecules from biomass-based starting compounds. Herein, we report an electrocatalytic Achmatowicz reaction for the synthesis of hydropyranones from furfuryl alcohols, which can be readily produced from biomass-derived and industrially available furfural. Taking advantage of photo-induced polymerization of a bipyridyl ligand, we demonstrate the facile preparation of a heterogenized nickel electrocatalyst, which effectively drives the Achmatowicz reaction electrochemically. A suite of characterization techniques and density functional theory computations were performed to aid the understanding of the reaction mechanism. It is rationalized that the unsaturated coordination sphere of nickel sites in our electrocatalyst plays an important role at low applied potential, not only allowing the intimate interaction between the nickel center and furfuryl alcohol but also enabling the transfer of hydroxide from nickel to the bound furfuryl alcohol.

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“…Their synthetic strategy involved an Achmatowicz reaction as the key step (Scheme 54). 110 An Achmatowicz reaction of furan derivative 201 was planned to provide enone 200 . This pyranone intermediate contains all the functionalities for elaboration to peloruside A.…”

Section: Introductionmentioning

confidence: 99%

Achmatowicz reaction and its application in the syntheses of bioactive molecules

Ghosh

Brindisi

2016

RSC Adv.

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Substituted pyranones and tetrahydropyrans are structural subunits of many bioactive natural products. Considerable efforts are devoted toward the chemical synthesis of these natural products due to their therapeutic potential as well as low natural abundance. These embedded pyranones and tetrahydropyran structural motifs have been the subject of synthetic interest over the years. While there are methods available for the syntheses of these subunits, there are issues related to regio and stereochemical outcomes, as well as versatility and compatibility of reaction conditions and functional group tolerance. The Achmatowicz reaction, an oxidative ring enlargement of furyl alcohol, was developed in the 1970s. The reaction provides a unique entry to a variety of pyranone derivatives from functionalized furanyl alcohols. These pyranones provide convenient access to substituted tetrahydropyran derivatives. This review outlines general approaches to the synthesis of tetrahydropyrans, covering general mechanistic aspects of the Achmatowicz reaction or rearrangement with an overview of the reagents utilized for the Achmatowicz reaction. The review then focuses on the synthesis of functionalized tetrahydropyrans and pyranones and their applications in the synthesis of natural products and medicinal agents.

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Toward the Synthesis of (+)-Peloruside A via an Intramolecular Vinylogous Aldol Reaction

Cited by 31 publications

References 35 publications

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

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

Electrocatalytic synthesis of heterocycles from biomass-derived furfuryl alcohols

Achmatowicz reaction and its application in the syntheses of bioactive molecules

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