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Reactions of Fluoroalkenes with an Aluminium(I) Complex
Author(s) -
Bakewell Clare,
White Andrew J. P.,
Crimmin Mark R.
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201802321
Subject(s) - alkene , chemistry , oxidative addition , yield (engineering) , reductive elimination , decomposition , medicinal chemistry , aluminium , monomer , photochemistry , stereochemistry , organic chemistry , catalysis , polymer , materials science , metallurgy
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.