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.

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An immobilized fluorous-tagged proline catalyst and its application as a recycling system in highly stereoselective asymmetric aldol reactions are described. The introduction of acidic sulfonamide groups bearing multifluorous tags at the carboxy position proved to be more effective than the introduction of bulky substituents on the proline backbone to achieve high stereoselectivity. The Teflon ® -immobilized proline catalyst could be recovered and reused at least five times while maintaining high levels of catalytic activity and stereoselectivity.