A bench-stable N-trifluoroacetyl nitrene equivalent for a simple synthesis of 2-trifluoromethyl oxazoles.

ortho-Nitro-substituted N-trifluoroacetyl imino-λ3-iodane is a bench-stable trifluoroacetyl nitrene precursor, in which intra- and intermolecular halogen bonding (XB) plays an important role. Potential synthetic applications of this novel precursor were explored.

Photo-Induced Aziridination of Alkenes with N-Sulfonyliminoiodinanes.

Activation of N-sulfonyliminiodinanes was achieved by photo-irradiation at 375 nm, which enabled the reaction with several alkenes to afford the corresponding aziridines. Mechanistic studies suggested that the reaction would proceed through a stepwise mechanism via radical intermediates rather than through a concerted process.

Photoactivated N-Acyliminoiodinanes Applied to Amination: an ortho-Methoxymethyl Group Stabilizes Reactive Precursors.

N-Acyliminoiodinanes were characterized for the first time by X-ray structural analysis. The ortho-methoxymethyl group and the carbonyl oxygen coordinate to the iodine atom of the iminoiodinane. Activation of the N-acyliminoiodinane was achieved by photoirradiation at 370 nm, thereby enabling reaction with various silyl enol ethers to give α-aminoketone derivatives in good to high yield. N-sulfonyliminoiodinanes bearing ortho substituents were used in photoinduced amination.