Aliphatic Claisen Rearrangement Promoted by Organoaluminium Reagents
TLDR
In this article, a 1-butyl-2-propenyl vinyl ether was treated with a hexane solution of Me3Al (1.0 M, 2.2 equiv) in CH2ClCH2Cl at 25 °C afforded 5-decen2-ol (91% yield, E⁄Z=47⁄53), which was produced by the [3,3] sigmatropic rearrangement and successive methylation.Abstract:
Organoaluminium compounds, R3Al, promote the Claisen rearrangement of allyl vinyl ether derivatives at room temperature under transfer of R or H as a nucleophile to the aldehydic carbon. Treatment of 1-butyl-2-propenyl vinyl ether with a hexane solution of Me3Al (1.0 M, 2.2 equiv) in CH2ClCH2Cl at 25 °C afforded 5-decen-2-ol (91% yield, E⁄Z=47⁄53), which was produced by the [3,3] sigmatropic rearrangement and successive methylation. The rearrangements with alkynylation, alkenylation, and hydrogenation are also achieved. The regular Claisen rearrangement products, or γ,δ-unsaturated aldehydes (ketones), are obtained at 25 °C in good to excellent yields with Et2AlSPh (2.5 equiv) or the combination of Et2AlCl (2.0 equiv) and PPh3 (2.2 equiv).read more
Citations
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Rare-earth metal triflates in organic synthesis
TL;DR: The main findings are: Lanthanide(II) Triflates in Organic Synthesis inorganic Synthesis 2295 10.2.1.
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Highly Chemoselective Catalytic Hydrogenation of Unsaturated Ketones and Aldehydes to Unsaturated Alcohols Using Phosphine-Stabilized Copper(I) Hydride Complexes
TL;DR: A base metal hydrogenation catalyst composed of the phenyldimethylphosphine-stabilized copper(I) hydride complex provides for the highly chemoselective hydrogenation of unsaturated ketones and aldehydes to unsaturated alcohols as discussed by the authors.
Journal ArticleDOI
Catalysis of the Claisen Rearrangement of Aliphatic Allyl Vinyl Ethers
Martin Hiersemann,Lars Abraham +1 more
TL;DR: The thermal Claisen rearrangement of allyl vinyl ethers is generally regarded as high-performance method for diastereoselective C−C bond formation.
Book ChapterDOI
7.2 – Claisen Rearrangements
TL;DR: In this paper, a survey of variants of the Claisen rearrangement that are of general use in stereoselective organic synthesis is presented, highlighting the influence of steric and electronic parameters on transition state geometries.
References
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Simple stereoselective version of the Claisen rearrangement leading to trans-trisubstituted olefinic bonds. Synthesis of squalene
William S. Johnson,Lucius Werthemann,William R. Bartlett,Timothy J. Brocksom,Tsung-Tee Li,D. John Faulkner,Michael R. Petersen +6 more
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Über Säureamidacetale, Harnstoffacetale und Lactamacetale
TL;DR: In this paper, a reaktionsfahigen reaktiver CH3-oder CH2-Gruppe unter Bildung von Aminoalkyliden-Verbindungen is discussed.