C-H functionalization of sp3 centers with Aluminum

A computational and mechanistic study of the baddeley reaction of Decalin

C.L. Lyall, M. Sato, M. Uosis-Martin, S.F. Asghar, Matthew Jones, I.H. Williams, Simon Lewis

Research output: Contribution to journalArticle

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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 languageEnglish
Pages (from-to)13745-13753
Number of pages9
JournalJournal of the American Chemical Society
Volume136
Issue number39
Early online date8 Sep 2014
DOIs
Publication statusPublished - 1 Oct 2014

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Aluminum
Hydrides
Friedel-Crafts reaction
Ions
Alkenes
Ether
Olefins
Protons
Ethers
decalin
aluminum chloride
acetyl chloride
hydronium ion

Cite this

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 journalArticle

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AU - Williams, I.H.

AU - Lewis, Simon

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