A novel intramolecular Diels–Alder approach to securinega alkaloids: formal synthesis of securinine

Honda, Toshio; Namiki, Hidenori; Kudoh, Mika; Watanabe, Naofumi; Nagase, Hiromasa; Mizutani, Hirotake

doi:10.1016/s0040-4039(00)00976-x

Cited by 25 publications

(6 citation statements)

References 10 publications

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“…The unfavorable influence of a carboxylate moiety in the tether has not deterred research using trienic esters in an IMDA key step, leading to complex natural products such as stenin 31 or securinin. 32 Our own results in comparable intermolecular examples prompted us to consider high pressure as a mild activation mode for the cycloaddition of the fragile dienol diethers 3. 19,21 A few cases of hyperbaric IMDA have been described, where the results show a limited but consistent increase of the diastereoselectivities.…”

Section: Intramolecular Cycloadditionsmentioning

confidence: 92%

Ring fission of chiral cyclic acetals plus intramolecular [4 + 2] cycloaddition: a sequential access to medium-size lactones. Application to the synthesis of carbasugars

Lemiègre¹,

Stevens²,

Combret³

et al. 2005

Org. Biomol. Chem.

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A set of alpha,beta-unsaturated cyclic acetals were reacted with t-butyllithium in THF. A conjugate elimination took place, triggering a ketal ring cleavage when two eq. of TMEDA were added to the medium. The lithium alcoholate thus obtained could be trapped in situ by 2,2,2-trifluoroethyl acrylate. The resulting acryloyl (1Z,3E)-dienyl ether was then submitted to an intramolecular Diels-Alder cycloaddition under high pressure (12 kbar, 50 degrees C). Depending on the structure of the linkage between the diene and the acrylate, the expected ("fused") lactones were obtained with total endo- or exo-selectivities and high to complete diastereoselectivities. A remarkable inversion of selectivity, from endo to exo, with respect to the stereochemical elements of the tether could be observed in these cases. A five step diastereoselective transformation of two of the resulting nine-membered ring lactones into modified carbasugars was finally achieved in 23% overall yield.

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Section: Intramolecular Cycloadditionsmentioning

confidence: 92%

Ring fission of chiral cyclic acetals plus intramolecular [4 + 2] cycloaddition: a sequential access to medium-size lactones. Application to the synthesis of carbasugars

Lemiègre¹,

Stevens²,

Combret³

et al. 2005

Org. Biomol. Chem.

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“…Given these attributes, it is unsurprising that the synthetic community has devoted significant attention to this collection of compounds,5 particularly to the challenges posed by the key shared domains within 1 – 5 . Indeed, since the inaugural total synthesis of securinine ( 1 ) by Horii in 1966,5a several other successful and highly creative approaches for forging their fused bicyclic butenolide domains have been disclosed, efforts that include selenoxide eliminations,5b,e,f,h,i,r intramolecular Wittig olefinations,5e,f,o,p,t–v ring‐closing metatheses,5j–p,s,x and alkylation of allylic bromides or mesylates 5a,h,i–m,q,t–v,x. However, most of these strategies require multiple steps to execute, typically constituting the longest (and least efficient) portion of the overall route.…”

Section: Methodsmentioning

confidence: 99%

An Efficient Approach to the Securinega Alkaloids Empowered by Cooperative N‐Heterocyclic Carbene/Lewis Acid Catalysis

et al. 2013

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Alles fügt sich zusammen: Die meisten der bisherigen Synthesen der Securinega‐Alkaloide erforderten längere Sequenzen zum Aufbau der verbrückenden Butenolid‐Domäne. Ein neuartiger Ansatz wird nun beschrieben, der mithilfe von N‐heterocyclischen Carbenen (NHCs) und Lewis‐Säuren die gesamte Domäne in einem einzigen Schritt aufbaut (siehe Schema). Die Synthese demonstriert, dass von Inalen abgeleitete Homoenolate als Nucleophile an intramolekularen Reaktionen teilnehmen können.

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“…The structure of securinine was confirmed by X-ray crystallography in 1965 . To date, one total and one formal synthesis of securinine have been reported. Additionally, preliminary accounts toward the total synthesis of securinine have been disclosed .…”

mentioning

confidence: 87%

An Approach to the Skeleton of the Securinega Alkaloids. The Total Synthesis of (±)-Securinine

2001

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A novel intramolecular Diels–Alder approach to securinega alkaloids: formal synthesis of securinine

Cited by 25 publications

References 10 publications

Ring fission of chiral cyclic acetals plus intramolecular [4 + 2] cycloaddition: a sequential access to medium-size lactones. Application to the synthesis of carbasugars

Ring fission of chiral cyclic acetals plus intramolecular [4 + 2] cycloaddition: a sequential access to medium-size lactones. Application to the synthesis of carbasugars

An Efficient Approach to the Securinega Alkaloids Empowered by Cooperative N‐Heterocyclic Carbene/Lewis Acid Catalysis

An Approach to the Skeleton of the Securinega Alkaloids. The Total Synthesis of (±)-Securinine

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