Wagner-Meerwein reaction

In Section 5.2.5, we discussed the Friedel-Crafts alkylation of benzene with 2-chloropentane. This reaction includes a Wagner-Meerwein reaction in conjunction with other elementary reactions. The Lewis acid catalyst A1C13 first converts the chloride into the 2-pentyl cation A (Figure 11.3). Cation A then rearranges into the isomeric 3-pentyl cation B, in part or perhaps to the extent that the equilibrium ratio is reached. The new carbenium ion B is not significantly more stable than the original one (A),... 

For a review of the Wagner-Meerwein reaction in a fundamental study on equilibria of different ring sizes, see ref. [5],... 

Cristol and his colleagues have contributed greatly to the understanding of the photochemical transformations of compounds which undergo light-induced solvolysis and photo-Wagner-Meerwein reactions. There are several other studies which are important additions to this body of work which are not covered in this review, and we refer the reader to these references [78-83]. 

Closely related to the Wagner-Meerwein reaction is the [1,2] rearrangement of vicinal diols and related substrates collectively referred to as pinacolic rearrangements2,319. Like the Wagner-Meerwein shift, the pinacol rearrangement proceeds via formation of an intermediate cation, followed by alkyl migration and concurrent generation of a carbonyl system. 

The Bamford-Stevens decomposition of tosylhydrazones by base has been applied to steroids, although not extensively. It has been demonstrated that the reaction proceeds via a diazo compound which undergoes rapid decomposition. The course of this decomposition depends upon the conditions in proton-donating solvents the reaction has the characteristics of a process involving carbonium ions, and olefins are formed, often accompanied by Wagner-Meerwein-type rearrangement. In aprotic solvents the diazo compound appears to give carbene intermediates which form olefins and insertion products ... 

Dehydration to olefins, which sometimes accompanies the reaction of alcohols with DAST [95, 108], is seldom as extensive as with a-fluoroamines (FAR and 1,1,2,3,3,3 hexafluoropropyldiethylamine) but occurs in a few cases to the exclusion of fluonnation, thus, 9a-fluoro-11-hydroxysteroids give 9a fluoro-A -steroids [127, 128] Dehydration accompanied by Wagner-Meerwein rearrangement occurs during the fluonnation of testosterone [129] Intermolecular dehydration to form ethers in addition to fluorides is observed in the reaction of benzhydryl alcohols [104] (Table 6)... 

From 5 the formation of alkene 2 is possible through loss of a proton. However, carbenium ions can easily undergo a Wagner-Meerwein rearrangement, and the corresponding rearrangement products may be thus obtained. In case of the Bamford-Stevens reaction under protic conditions, the yield of non-rearranged olefins may be low, which is why this reaction is applied only if other methods (e.g. dehydration of alcohols under acidic conditions) are not practicable. 

Except for terpene chemistry, the Wagner-Meerwein rearrangement is of limited synthetic importance. It is rather found as an undesired side-reaction with other reactions, for example in the synthesis of alkenes by elimination reactions. 

It was mentioned above that even alkanes undergo Wagner-Meerwein rearrangements if treated with Lewis acids and a small amount of initiator. An interesting application of this reaction is the conversion of tricyclic molecules to adamantane and its derivatives. It has been found that all tricyclic alkanes containing 10 carbons are converted to adamantane by treatment with a Lewis acid such as AICI3. If the substrate contains more than 10 carbons, alkyl-substituted adamantanes are produced. The lUPAC name for these reactions is Schleyer adamantization. Two examples are... 

An elimination/double Wagner-Meerwein rearrangement process has recently been developed by Langer and coworkers [39]. Treatment of compound 1-136, obtained by reaction of 1-134 and 1-135, with trifluoroacetic acid (TFA) led to the cationic species 1-137, which then underwent a twofold Wagner-Meerwein rearrangement to give the bicydic compound 1-139 via 1-138 (Scheme 1.34). 

Scheme 1.34. Domino elimination/double Wagner-Meerwein rearrangement reaction.

Reactions. Part. I. The Mechanism of the Wagner-Meerwein Rearrangement. Exchange of Radioactive Chlorine and of Deuterium between Camphene Hydrochloride and Hydrogen Chloride. J. chem. Soc. [London] 1939, 1188. 

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