title: C-H functionalization of sp(3) centers with aluminum: a computational and mechanistic study of the Baddeley reaction of decalin.
abstract: Decalin undergoes reaction with aluminum trichloride and acetyl chloride to form a tricyclic enol ether in good yield, as first reported by Baddeley. This eye-catching transformation, which may be considered to be an aliphatic Friedel-Crafts reaction, has not previously been studied mechanistically. Here we report experimental and computational studies to elucidate the mechanism of this reaction. We give supporting evidence for the proposition that, in the absence of unsaturation, an acylium ion acts as a hydride acceptor, forming a tertiary carbocation. Loss of a proton introduces an alkene, which reacts with a further acylium ion. A concerted 1,2-hydride shift/oxonium formation, followed by elimination, leads to formation of the observed product.
authors.affiliation: Department of Chemistry, University of Bath , Bath, U.K. BA2 7AY.
authors.forename: Catherine L
authors.initials: CL
authors.lastname: Lyall
authors.forename: Makoto
authors.initials: M
authors.lastname: Sato
authors.forename: Mario
authors.initials: M
authors.lastname: Uosis-Martin
authors.forename: Syeda Farina
authors.initials: SF
authors.lastname: Asghar
authors.forename: Matthew D
authors.initials: MD
authors.lastname: Jones
authors.forename: Ian H
authors.initials: IH
authors.lastname: Williams
authors.forename: Simon E
authors.initials: SE
authors.lastname: Lewis