Unprecedented Asymmetric Epoxidation of Isolated Carbon–Carbon Double Bonds by a Chiral Fluorous Fe(III) Salen Complex: Exploiting Fluorophilic Effect for Catalyst Design

Abstract

The first asymmetric epoxidation of isolated carbon–carbon double bonds by a chiral salen complex using ubiquitous Fe(III) as a center‐metal is described. By simultaneously introducing fluorous tags and tert‐butyl groups into the ligand of the salen complex, asymmetric epoxidation is achieved. The fluorous tags act as both the electron‐withdrawing groups, to improve the catalytic activity for oxidation, and the driving force to form a unique asymmetric stereo environment. Crystallographic analysis of the complex revealed that the catalyst has a distinctive umbrella structure based on intramolecular fluorophilic effect. This is the first example of asymmetric catalytic space construction that exploits fluorous space‐interaction of neighboring fluorous tags.