3 research outputs found
C-H functionalization of sp<sup>3</sup> centers with Aluminum:A computational and mechanistic study of the baddeley reaction of Decalin
C–H Functionalization of sp<sup>3</sup> Centers with Aluminum: A Computational and Mechanistic Study of the Baddeley Reaction of Decalin
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