Stereochemistry in the oxidation of primary amines to nitro compounds by dimethyldioxirane

Article abstract of DOI:10.1016/0957-4166(96)00195-4

Oxidation of the chiral amines, (+) and (-)-isopinocampheylamine, with dimethyldioxirane (1) gives the corresponding nitro compounds with retention of configuration at the amine-hearing carbon atom. When lower amounts of I are used in the oxidation the amines give the nitroso dimers as the major products. Treatment of the nitroso dimer from the (-)-amine with additional 1 gave the same nitro compound as obtained from the amine oxidation. To further indicate that no racemization occurs during the amine oxidation we have synthesized the oxime of the nitroso intermediate and shown that it does not tautomerize under the reaction conditions.