Preparation and Reactions of Cyclic α-Nitroketones

The preparations, chemical properties, and reactions of cyclic α-nitroketones are reviewed. Those compounds which possess an α-hydrogen atom can form salts. The carbonyl, nitro, and α′-methylene groups can be converted to other functional groups. Because the activated C-C bond between the carbonyl group and the nitrosubstituted carbon atom can be cleaved by nucleophilic reagents, it is possible to synthesise, e.g. ω-nitrocarboxylic acids, α,ω-dicarboxylic acids and derivatives thereof, arylnitromethanes, and α, ω-dinitroalkanes. 2-Nitrocyclohexanone is of interest for the industrial production of ε-caprolactam and L-lysine. 1. Introduction 2. Preparation of Cyclic α-Nitroketones 2.1. Reactions Starting from Cyclic Ketones, Enol Esters, or Enol Silyl Ethers 2.2. Reactions Starting from Cycloalkenes 2.3. Cyclisation Reactions 2.4. Miscellaneous Preparations 3. Properties of Cyclic α-Nitroketones 4. Reactions of Cyclic α-Nitroketones 4.1. Salt Formation and Reactions at the α-Hydrogen Atom 4.2. Reactions at the Carbonyl, Nitro, and α′-Methylene Groups 4.3. Ring Cleavage of Cyclic α-Nitroketones