Alkene Syn- and Anti-Oxyamination with Malonoyl Peroxides

Malonoyl peroxide 6 is an effective reagent for the syn- or anti-oxyamination of alkenes. Reaction of 6 and an alkene in the presence of O-tert-butyl-N-tosylcarbamate (R3 = CO2tBu) leads to the anti-oxyaminated product in up to 99% yield. Use of O-methyl-N-tosyl carbamate (R3 = CO2Me) as the nitrogen nucleophile followed by treatment of the product with trifluoroacetic acid leads to the syn-oxyaminated product in up to 77% yield. Mechanisms consistent with the observed selectivities are proposed.