Cycloaddition of Dialkylalumanyl Anion toward Unsaturated Hydrocarbons in (1+2) and (1+4) Modes

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.
ファイル公開：2021-02-17