The Nitrosation of Aliphatic Carbon Atoms

Abstract

The nitrosation reaction consists in the replacement of a hydrogen atom by the nitroso group with the formation of a nitroso or oximo derivative. With a few exceptions, the replacement of hydrogen on an aliphatic carbon atom requires the presence of an electron‐attracting groups adjacent to the carbon to be nitrosated. Acyl, aroyl, carbonyl, carboxy, carbalkoxyl, nitrogen, cyano, imino, and aryl groups may serve as activators. Monoketones are readily converted into alpha‐oximino ketones, whereas monoesters containing no other activating groups do not undergo the reaction. Victor Meyer discovered the reaction in 1873–1874.

Enolate-Based Regioselective Anti-Beckmann C–C Bond Cleavage of Ketones

“…Lithium, sodium, potassium, and to a lesser extent magnesium enolates undergo facile oxidative cleavage by organic nitrites provided THF is used as solvent. The ease of nitrosative cleavage of preformed enolates in THF is in stark contrast with the more common use of alkyl nitrites for α-hydroxyimination of enolizable ketones, which is usually conducted in water or alcoholic solvents using alkoxide bases. ,, The critical role of the solvent for the product distribution can be explained by the reduced nucleophilicity of the solvated metal alkoxide and the ease of nitroso ketone tautomerization in protic solvents. Cleavage is in these solvents only observed if the intermediate α-nitroso ketone does not bear tautomerizable protons as in Woodward’s quinine total synthesis or in Yamamoto’s fragmentation reactions …”

2,6,6-Trimethylcyclohexene-1-carbaldehyde oxime

“…For applications of oximes in organic syntheses, see: Cerny et al (1969); Donaruma & Heldt (1960); Kutney et al (1992); Touster (1953). For graph-set notation, see: Etter et al (1990); Bernstein et al (1995).…”

“…Moreover oximes are used for the preparation of many compounds such as amines by reduction (Cerny et al, 1969), nitro compounds by oxidation, amides by the Beckmann rearrangement and carbonyl compounds from non carbonyl compounds (Touster, 1953). The title compound C 10 H 17 NO is a key intermediate in the synthesis of aroma compounds such as β-cyclogeranyl nitrile which can be used for the synthesis of the important aroma compound β-damascone (Kutney et al, 1992).…”

Deprotection of oximes, imines, and azines to the corresponding carbonyls using Cu-nanoparticles on cellulose template as green reusable catalyst

“…2 Oximes, imines, and azines are frequently used as protecting groups for carbonyls because they provide relatively stable compounds compared to others. These compounds can also be prepared from the sources other than carbonyls, such as alcohols, 3 amines, 4 nitriles, 5 nitroalkanes, 6 and azaarenes, 7 which sometimes provide newer synthetic avenues for the selective insertion of aldehydes and ketones. There are numerous methodologies reported for the deprotection of oximes and related compounds.…”