Aliphatic Claisen rearrangement promoted by organoaluminium reagents.
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概要
- 論文の詳細を見る
Organoaluminium compounds, R<SUB>3</SUB>Al, 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<SUB>3</SUB>Al (1.0 M, 2.2 equiv) in CH<SUB>2</SUB>ClCH<SUB>2</SUB>Cl at 25 °C afforded 5-decen-2-ol (91% yield, <I>E</I>⁄<I>Z</I>=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 Et<SUB>2</SUB>AlSPh (2.5 equiv) or the combination of Et<SUB>2</SUB>AlCl (2.0 equiv) and PPh<SUB>3</SUB> (2.2 equiv).
- 公益社団法人 日本化学会の論文
著者
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Takai Kazuhiko
Department Of Applied Chemistry Faculty Of Engineering Okayama University
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Mori Ichiro
Department Of Cardiology The University Of Tokyo
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Nozaki Hitosi
Department of Industrial Chemistry, Faculty of Engineering Kyoto University
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Oshima Koichiro
Department of Chemistry, Massachusetts Institute of Technology
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