Synthesis, structure, and transformations of N-(alkyl-, benzyl-, arylsulfonyl)-N-(oxiran-2-ylmethyl)bicyclo[2.2.1]hept-5-en-exo-2-ylmethanamines

Reactions of N-(alkyl-, benzyl-, arylsulfonyl)bicyclo[2.2.1]hept-5-en-exo-2-ylmethanamines with 2-(chloromethyl)oxirane in the presence of tetramethylammonium iodide gave a number of cage-like N-(oxiran-2-ylmethyl)sulfonamides, as well as N-(exo-5,6-epoxybicyclo[2.2.1]heptan-exo-2-ylmethyl)-4-nitro-N-(oxiran-2-ylmethyl)benzenesulfonamide. The latter was also synthesized by oxidation of oxiran-2-ylmethyl norbornene derivative with peroxy acids. Opening of the epoxide ring in N-(oxiran-2-ylmethyl) sulfonamides in reaction with benzylamine followed the Krasuskii rule, and the aminolysis of N-(exo-5,6-epoxybicyclo[2.2.1]-heptan-exo-2-ylmethyl)-4-nitro-N-(oxiran-2-ylmethyl)benzenesulfonamide chemoselectively occurred at the side-chain epoxy group.