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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
Cycloaddition of Dialkylalumanyl Anion toward Unsaturated Hydrocarbons in (1+2) and (1+4) Modes
Kengo Sugita1, Ryo Nakano1, Makoto Yamashita1
1Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8603 Aichi, Japan.
Abstract:
The reactivity of dialkylalumanyl anion (1) towards naphthalene, anthracene, diphenylacetylene, and (E)/(Z)-stilbenes was investigated. The compound 1 reacts with naphthalene and anthracene through (1+4) cyclization, giving Al-containing norbornadiene derivatives. In the reaction of 1 with diphenylacetylene and (E)/(Z)-stilbenes, (1+2) cyclization proceeded to form Al-C-C three-membered rings. Cyclization toward (E)- or (Z)-stilbenes solely gave a trans-cycloadduct. DFT calculations revealed that the cycloaddition of 1 with (Z)-stilbene proceeds via a single transition state with a carbanion character, which results in the selectivity towards the trans-cycloadduct.
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