ALIPHATIC CLAISEN REARRANGEMENT PROMOTED BY ORGANOALUMINIUM REAGENTS.

Kazuhiko Takai, Ichiro Mori, Koichiro Oshima, Hitosi Nozaki

Research output: Contribution to journalArticle

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Abstract

Organoaluminium compounds, R//3Al, 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 Me//3Al (1. 0 M, 2. 2 equiv) in CH//2ClCH//2Cl at 25 degree C afforded 5-decen-2-ol (91% yield, E/Z equals 47/53), which was produced by the left bracket 3,3 right bracket sigmatropic rearrangement and successive methylation. The rearrangements with alkynylation, alkenylation, and hydrogenation are also achieved. The regular Claisen rearrangement products, of gamma , delta -unsaturated aldehydes (ketones), are obtained at 25 degree C in good to excellent yields with Et//2AlSPh (2. 5 equiv) or the combination of Et//2AlCl (2. 0 euiv) and PPh//3 (2. 2 equiv).

Original languageEnglish
Pages (from-to)446-451
Number of pages6
JournalBulletin of the Chemical Society of Japan
Volume57
Issue number2
Publication statusPublished - Feb 1984
Externally publishedYes

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Alkenylation
Nucleophiles
Methylation
Hexanes
Ketones
Aldehydes
Hydrogenation
Carbon
Derivatives
Temperature
vinyl ether

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

ALIPHATIC CLAISEN REARRANGEMENT PROMOTED BY ORGANOALUMINIUM REAGENTS. / Takai, Kazuhiko; Mori, Ichiro; Oshima, Koichiro; Nozaki, Hitosi.

In: Bulletin of the Chemical Society of Japan, Vol. 57, No. 2, 02.1984, p. 446-451.

Research output: Contribution to journalArticle

Takai, Kazuhiko ; Mori, Ichiro ; Oshima, Koichiro ; Nozaki, Hitosi. / ALIPHATIC CLAISEN REARRANGEMENT PROMOTED BY ORGANOALUMINIUM REAGENTS. In: Bulletin of the Chemical Society of Japan. 1984 ; Vol. 57, No. 2. pp. 446-451.
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