Favorskii-like mechanism

The mechanism of the novel transformation of a-nitro- to a-hydroxy-ketones has been probed. The reaction, which proceeds under basic aqueous conditions, requires that the Q -nitro substrate be CH-acidic in the a -position, and that it be readily depro-tonated under the conditions employed. NO2 -OH exchange occurs with retention of configuration, with the hydroxyl oxygen being predominantly derived from the solvent. A mechanism involving neighbouring-group participation, via a Favorskii-like cyclopropanone intermediate, is proposed. 

Although experimental evidence makes it unlikely that the latter has any general relevance to Favorskii reactions, it is included for consideration here because it appears as a likely mechanism in the special case of 5a,7a-dibromocholestan-6-one (31) [3iy]. This compound undergoes a ring contraction on treatment with pyridine to give the unsaturated carboxylic... 

Dienone-phenol rearrangements are mechanistically diverse. They may involve 1,2-shifts of the Wag-ner-Meerwein type, or of the benzil-benzilic acid kind 1,3-shifts by a Claisen-Cope mechanism 1,5-sigmatropic shifts Favorskii-like reactions and other types. They may also be induced photochemically. A number of reviews are available, which discuss mechanistic aspects in detail. In this chapter emphasis is put on preparative aspects of these reactions and the examples are organized on a structural basis, stressing the new bond(s) formed. 

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