An Efficient Route to Both Enantiomers of N-(p-Tolylsulfonyl)benzenesulfonimidamide and Their Use for Asymmetric Allylic Amination of Olefins

The chiral compounds (R)- and (S)-N-(p-tolylsulfonyl)benzenesulfonimidamide have been prepared efficiently from N-(p-tolylsulfonyl)benzenesulfonimidoyl chloride and both enantiomers were transformed into chiral selenium diimide reagents, (S)- and (R)-N,N′-bis[N-(p-tolylsulfonyl)benzenesulfonimidoyl]selenium diimide, respectively, for the asymmetric allylic amination of olefins. Asymmetric allylic amination of methylenecyclohexane with the S-configured selenium diimide reagent afforded allylic amide, (1S)-N-[(R)-N-(p-tolylsulfonyl)benzenesulfonimidoyl]-2-methylenecyclohexylamine as a major diastereomer (42% diastereomeric excess). Similarly, cyclohexene, 1-heptene, and cyclooctene gave chiral allylic amides with 34%, 32%, and 20% diastereomeric excess, respectively. It is apparent that the S-configured diimido selenium reagent gives S-configured allylic amides, and that the R-configured reagent affords R-configured allylic amides as the major diastereomers in all of the cases investigated.