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.
Original language | English |
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Pages (from-to) | 13745-13753 |
Number of pages | 9 |
Journal | Journal of the American Chemical Society |
Volume | 136 |
Issue number | 39 |
Early online date | 8 Sep 2014 |
DOIs | |
Publication status | Published - 1 Oct 2014 |
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High Performance Computing (HPC) Facility
Steven Chapman (Manager)
University of BathFacility/equipment: Facility
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MC2-Mass Spectrometry (MS)
Material and Chemical Characterisation (MC2)Facility/equipment: Technology type
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MC2- Nuclear Magnetic Resonance (NMR)
Material and Chemical Characterisation (MC2)Facility/equipment: Technology type