Halogen Bond Catalysis on Carbonyl–OlefinRing‐ClosingMetathesis Reaction: Comparison with Lewis Acid Catalysis

Abstract

Comprehensive SummaryThe carbonyl–olefin ring‐closing metathesis reactions have become a powerful tool for carbon‐carbon bond formation. In this work, the halogen bond catalysis and classical Lewis acid catalysis on the carbonyl–olefin ring‐closing metathesis reaction were investigated by density function theory. For both the halogen bond catalysis and classical Lewis acid catalysis, the carbonyl–olefin ring‐closing metathesis reaction occurs by [2 + 2]‐cycloaddition process and [2 + 2]‐cycloreversion process, the reaction energy barriers are low, therefore, it can be performed easily at room temperature. The essential difference of the two kinds of catalysts is that the catalytic mechanism of halogen bond catalysis is mainly contribution of electrostatic interaction, while that of classical Lewis acid catalysis is mainly catalyzed by orbital interaction. The halogen bond donor catalysts (ICl3, IF3) are expected to be efficient catalysts for the reaction and further promote the chemical synthesis of carbonyl–olefin ring‐closing metathesis reaction.