Zinc halides: acetalization catalysts

Because of the high nucleophilicity and reactivity of diazoalkanes, catalytic decomposition occurs readily, not only with a wide range of transition metal complexes but also with Brpnsted or Lewis acids. Well-established catalysts for diazodecomposition include zinc halides [638,639], palladium(II) acetate [640-642], rhodium(II) carboxylates [626,643] and copper(I) triflate [636]. Copper(II)... 

The yield of the arylcyclopropanes is very sensitive to the catalyst employed. Very low yields (< 10%) were observed when lithium salts were employed. Magnesium, cobalt and copper salts gave better results, but the best results were achieved with zinc halides and rho-dium(II) acetate. This was apparent when 7-phenylbicyclo[4.1. OJheptane (4) was prepared from cyclohexene and phenyldiazomethane. ... 

One of the most general approaches to the synthesis of this type of compounds involves the Lewis acid promoted rearrangement of acetals of a-substituted propiophenones [4,5]. Besides silver salts, a large variety of soft and borderline Lewis acids have been found to be convenient catalysts for the 1,2-aryl shift, noticeably zinc halides in substoichiometric amounts [6]. As final products need to be free of metal traces for human consume, the use of Lewis acids supported on microporous solids can be advantageous since a better recovering of the catalyst can be anticipated. 

Ion 21 can either lose a proton or combine with chloride ion. If it loses a proton, the product is an unsaturated ketone the mechanism is similar to the tetrahedral mechanism of Chapter 10, but with the charges reversed. If it combines with chloride, the product is a 3-halo ketone, which can be isolated, so that the result is addition to the double bond (see 15-45). On the other hand, the p-halo ketone may, under the conditions of the reaction, lose HCl to give the unsaturated ketone, this time by an addition-elimination mechanism. In the case of unsymmetrical alkenes, the attacking ion prefers the position at which there are more hydrogens, following Markovnikov s rule (p. 984). Anhydrides and carboxylic acids (the latter with a proton acid such as anhydrous HF, H2SO4, or polyphosphoric acid as a catalyst) are sometimes used instead of acyl halides. With some substrates and catalysts double-bond migrations are occasionally encountered so that, for example, when 1 -methylcyclohexene was acylated with acetic anhydride and zinc chloride, the major product was 6-acetyl-1-methylcyclohexene. ... 

Alkenes react with acyl halides or acid anhydrides in the presence of Lewis acid catalysts. The reaction works better with cyclic alkenes than for acyclic ones. A mechanistically significant feature of this reaction is the kinetic preference for formation of unsaturated ketones. Mechanistic studies using acetic anhydride and zinc chloride as the reagent system are consistent with a two-step mechanism in which the location of the double bond in the product is determined by ease of deprotonation of the initial adduct. A related reaction occurs when alkenes react... 

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