Reactions of Fluoroalkenes with an Aluminium(I) Complex

A series of industrially relevant fluoroalkenes react with a monomeric Al I complex. These reactions break strong sp 2 and sp 3 C−F bonds, and result in the formation of a diverse array of organoaluminium compounds. Mechanistic studies show that two mechanisms are likely in operation: 1) direct oxidative addition of the C−F bond to Al I occurs with retention of alkene stereochemistry, and 2) stepwise formation and decomposition of a metallocyclopropane intermediate occurs with inversion of alkene stereochemistry. As part of this mechanistic analysis, we have isolated the first aluminium metallocyclopropane complex from oxidative addition of an alkene to Al I . Remarkably this reaction is reversible and reductive elimination of the alkene occurs at higher temperature reforming Al I . Furthermore, in selected cases the organoaluminium products are susceptible toward β‐fluoride elimination to yield a double C−F activation pathway.