Fe‐Catalyzed Stereospecific Intramolecular Friedel–Crafts‐type Reaction of Fluoroalkyl Cyclopropyl Carbinols via Non‐classical Carbocation

Abstract Here we describe a Fe‐catalyzed stereospecific intramolecular Friedel–Crafts‐type reaction of polysubstituted stereodefined fluoroalkyl cyclopropyl carbinols. This transformation provides access to a series of fluoroalkyl group‐substituted dihydro‐1 H ‐indenols bearing three continuous stereogenic centers including two congested tetra‐substituted stereocenters. The key to the realization of this reaction relies on the electronic destabilizing effect of fluoroalkyl group to tune the stability and reactivity of non‐classical cyclopropyl‐carbinyl cation intermediate. Functional group interconversions of the obtained diastereomerically pure dihydro‐1 H ‐indenols further demonstrated the synthetic utility of this rationally designed reaction.