Aliphatic Friedel Crafts Research Articles

C-H functionalization of sp(3) 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.

Aliphatic C–H activation with aluminium trichloride–acetyl chloride: expanding the scope of the Baddeley reaction for the functionalisation of saturated hydrocarbons

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.

Scope and limitations of aliphatic Friedel-Crafts alkylations. Lewis acid catalyzed addition reactions of alkyl chlorides to carbon-carbon double bonds

Lewis acid catalyzed addition reactions of alkyl halides 1 with unsaturated hydrocarbons 2 have been studied. 1:l addition products 3 are formed if the addends 1 dissociate faster than the corresponding products 3; otherwise, polymerization of 2 takes place. For reaction conditions under which 1 and 3 exist mainly undissociated, solvolysis constants of model compounds can be used to predict the outcome of any such addition reactions if systems with considerable steric hindrance are excluded.

ChemInform Abstract: ALIPHATIC FRIEDEL‐CRAFTS ACYLATION OF VINYL SILANES

AbstractTrimethylsilylstyrol (I) reagiert mit Benzoylchlorid zum Chlorketon (II) und Substitutionsprodukt (III).

Aliphatic Friedel–Crafts acylation of vinyl silanes

Some vinyltrimethylsilanes give high yields of substitution products in aliphatic Friedel–Crafts acylation and the reaction is site-selective, acylation taking place at the carbon atom carrying the trimethylsilyl group.

Aliphatic Friedel–Crafts reactions. Part IX. Acetylation of cis-cyclooctene

The effect of catalyst on the acetylation of cis-cyclo-octene and the occurrence of a transannular hydride shift in the intermediate carbonium ion are reported. Stannic chloride as catalyst affords 1-acetylcyclo-octene, whilst boron trifluoride or zinc chloride affords 4-acetylcyclo-octene. Aluminium chloride yields 1-acetyl-4-chlorocyclo-octene or 4-acetyl-1-ethylcyclohexene according to the catalyst activity.

Aliphatic Friedel–Crafts reactions. Part X. Preparation of 1-acylbicyclo[4,2,0]octanes

Acylation of cis-cyclo-octene affords 1-acyl-4-chlorocyclo-octanes in good yield. Dehydrohalogenation of these compounds with potassium t-butoxide readily affords the corresponding 1-acylbicyclo[4,2,0]octanes. A synthesis of bicyclo[4,2,0]octan-1-ol is reported.

435. Aliphatic Friedel–Crafts reactions. Part V. Further acylations of cyclopentene, cyclohexene, and cycloheptene

The first page of this article is displayed as the abstract.

257. Aliphatic Friedel–Crafts reactions. Part III. The acylation of cycloheptene and cyclo-octene

The first page of this article is displayed as the abstract.

258. Aliphatic Friedel–Crafts reactions. Part IV. The preparation of divinyl ketones

258. Aliphatic Friedel–Crafts reactions. Part IV. The preparation of divinyl ketones

807. Aliphatic Friedel–Crafts reactions. Part II. The acylation of cyclopentene

807. Aliphatic Friedel–Crafts reactions. Part II. The acylation of cyclopentene

Aliphatic Friedel—Crafts Reactions. I. The Alkylation of Butanes by Methyl and Ethyl Bromide

Aliphatic Friedel—Crafts Reactions. I. The Alkylation of Butanes by Methyl and Ethyl Bromide