Rearrangement Reactions of Alcohols, Enols, and Phenols

Another group of rearrangement reactions of alcohols, enols, and phenols results in the formation of compounds in which the hydroxyl group (-OH) or its equivalent 

Some of these reactions are presented in Table 8.7 and are discussed subsequently. 

One way to examine this problem has already been addressed in the previous chapter. Thus, if the migration of the hydrogen ( H) is part of the rate-determining process, then the reaction with should be faster than with (breaking a carbon-hydrogen bond is easier than breaking a carbon-deuterium bond) and the ratio of 

TABLE 8.7. Some Rearrangement Reactions of Alcohols, Enols, Phenols, and Their Derivatives 

Product of solvolysis of the toluenesulfonate (tosylate) ester in ethanoic acid (acetic acid, CH3CO2H) Products of solvolysis of the toluenesulfonate (tosylate) ester in ethanoic acid (acetic acid, CH3CO2H) Chiral reactant yields racemic product 

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Part I. The Reactions of Alcohols, Enols, and Phenols Oxidation, Reduction, Substitution, Addition, Elimination, and Rearrangement Part II. Ethers... 

Cross-conjugated dienones are quite inert to nucleophilic reactions at C-3, and the susceptibility of these systems to dienone-phenol rearrangement precludes the use of strong acid conditions. In spite of previous statements, A " -3-ketones do not form ketals, thioketals or enamines, and therefore no convenient protecting groups are available for this chromophore. Enol ethers are not formed by the orthoformate procedure, but preparation of A -trienol ethers from A -3-ketones has been claimed. Another route to A -trien-3-ol ethers involves conjugate addition of alcohol, enol etherification and then alcohol removal from la-alkoxy compounds. 

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