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Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Homogeneous Sc(OTf)3-Catalyzed Direct Allylation Reactions of General Alcohols with Allylsilanes
Yuanjun Di1, Tsutomu Yoshimura1, Shun-Ichi Naito1
1Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, and Center for the Promotion of Interdisciplinary Education and Research, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan.
Abstract:
Homogeneous Sc(OTf)3 used in nitromethane showed excellent catalytic activity for the direct allylation reactions of general alcohols including benzylic, propargylic, allylic, and some aliphatic alcohols with allyltrimethylsilane under mild and neutral reaction conditions. Metal-free β-silyl-substituted carbocations are intermediates generated by the highly oxophilic Sc(OTf)3-assisted rapid removal of a hydroxyl group in alcohols, which is supported by the result that allylation of (R)-1-(naphthalen-2-yl)ethan-1-ol with allytrimethylsilanes using the Sc(OTf)3 catalyst combined with (R)- or (S)-[1,1'-binaphthalene]-2,2'-diol ligands gave only racemic 2-(pent-4-en-2-yl)naphthalene in quantitative yield. The present study resolves the argument about the uncertain catalytic activity of Sc(OTf)3.
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