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.

Study of the crystal structures of the title compounds reveals that the solid-state photochemical nitro–nitrito linkage isomerization is restricted by inter­molecular C—H⋯O,O contacts in the 3-hy­droxy­pyridine phase.

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Table of contents……………………………………………………………...…S1 I. Chemicals and instruments……………………………………………..……S2 II. Ring-closing metathesis reactions of 8 in CDCl 3 ……………………..……..S3 III. Ring-closing metathesis reactions of 10………………………………..……S3 IV. Synthesis of catalysts 1b-1g…………………………………………………S4-S19 V. UV-Vis spectrums of bidentate ligand precursors of 1f and 1g…………..…S20 VI. Noesy spectrums of 7f and 1f………………………………………………S21-S22 VII. Molecular orbital calculation (B3LYP/LAN2DZ)………………………..S23-S25 VIII. References………….………………………………………………………S26 IX. Spectral data for products…………………………………………………....S27-S61 S2 I. Chemicals and instruments All laboratory chemicals were purchased from Wako, TCI, Aldrich and Kanto Kagaku, used without further purification. Solvents were removed by rotary evaporation under reduced pressure using a 40 ºC water bath. Non-volatile compounds were dried in vacuo at 0.01 mbar. All reactions were stirred magnetically and monitored by thin layer chromatography (TLC) using silica gel plates. Purification by chromatography was performed on silica gel (45-75 µm). NMR spectra were recorded with JEOL