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

Published in: Chemistry (Weinheim an der Bergstrasse, Germany) (2020)

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.

Keyphrases

density functional theory
ionic liquid
molecular dynamics
molecular dynamics simulations
single cell
molecular docking
atomic force microscopy
mass spectrometry
structure activity relationship