4752-31-2Relevant academic research and scientific papers
C-H functionalization of sp3centers with aluminum: A computational and mechanistic study of the baddeley reaction of decalin
Lyall, Catherine L.,Sato, Makoto,Uosis-Martin, Mario,Asghar, Syeda Farina,Jones, Matthew D.,Williams, Ian H.,Lewis, Simon E.
supporting information, p. 13745 - 13753 (2015/02/05)
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.
Aliphatic C-H activation with aluminium trichloride-acetyl chloride: Expanding the scope of the Baddeley reaction for the functionalisation of saturated hydrocarbons
Lyall, Catherine L.,Uosis-Martin, Mario,Lowe, John P.,Mahon, Mary F.,Panto?, G. Dan,Lewis, Simon E.
, p. 1468 - 1475 (2013/05/21)
The functionalisation of decalin by means of an "aliphatic Friedel-Crafts" reaction was reported over fifty years ago by Baddeley et al. This protocol is of current relevance in the context of C-H activation and here we demonstrate its applicability to a range of other saturated hydrocarbons. Structural elucidation of the products is described and a mechanistic rationale for their formation is presented. The "aliphatic Friedel-Crafts" procedure allows for production of novel oxygenated building blocks from abundant hydrocarbons and as such can be considered to add significant synthetic value in a single step.
