Abstract
| Original language | English |
|---|---|
| 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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C-H functionalization of sp3 centers with Aluminum : A computational and mechanistic study of the baddeley reaction of Decalin. / Lyall, C.L.; Sato, M.; Uosis-Martin, M.; Asghar, S.F.; Jones, Matthew; Williams, I.H.; Lewis, Simon.
In: Journal of the American Chemical Society, Vol. 136, No. 39, 01.10.2014, p. 13745-13753.Research output: Contribution to journal › Article
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TY - JOUR
T1 - C-H functionalization of sp3 centers with Aluminum
T2 - A computational and mechanistic study of the baddeley reaction of Decalin
AU - Lyall, C.L.
AU - Sato, M.
AU - Uosis-Martin, M.
AU - Asghar, S.F.
AU - Jones, Matthew
AU - Williams, I.H.
AU - Lewis, Simon
PY - 2014/10/1
Y1 - 2014/10/1
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=84907564309&partnerID=8YFLogxK
UR - http://dx.doi.org/10.1021/ja5062246
U2 - 10.1021/ja5062246
DO - 10.1021/ja5062246
M3 - Article
VL - 136
SP - 13745
EP - 13753
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 39
ER -