Bakewell, C; White, AJP; Crimmin, MR; (2018) Reactions of Fluoroalkenes with an Aluminium(I) Complex. Angewandte Chemie International Edition , 57 (22) pp. 6638-6642. 10.1002/anie.201802321.

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Abstract

A series of industrially relevant fluoroalkenes react with a monomeric Al¹ complex. These reactions break strong sp² and sp³ 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 Al¹ 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 Al¹. Remarkably this reaction is reversible and reductive elimination of the alkene occurs at higher temperature reforming Al¹. Furthermore, in selected cases the organoaluminium products are susceptible toward β‐fluoride elimination to yield a double C−F activation pathway.

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