Asymmetric syntheses with BINOL-based imidoyl azide

Thermal decomposition of 2,4,6-trimethylphenyl and (+)-2′-methoxy-1,1′-binaphthalen-2-yl (4-methylphenylsulfonyl)azidimidocarbonates in the presence of norbornene, methyl acrylate, and camphene was studied. (+)-2′-Methoxy-1,1′-binaphthalen-2-yl (4-methylphenylsulfonyl)azidimidocarbonate reacted with norbornene to give (+)- exo -2′-methoxy-1,1′-binaphthalen-2-yl N -(4-methylphenylsulfonyl)-3-azatricyclo-[3.2.1.0 2,4 ]octane-3-carboximidoate, while in the reaction with methyl acrylate a mixture of stereoisomeric methyl 1-[(2′-methoxy-1,1′-binaphthalen-2-yloxy)(4-methylphenylsulfonylimino)methyl]aziridine-2-carboxylates was obtained. The reaction of 2,4,6-trimethylphenyl (4-methylphenylsulfonyl)azidimidocarbonate with (−)-camphene involved insertion of intermediate nitrene into the exocyclic double bond with formation of 2,4,6-trimethylphenyl N -(3,3-dimethylbicyclo[2.2.1]heptan-2-ylidenemethyl)- N ′-(4-methylphenylsulfonyl)-imidocarbamate as a 3: 1 mixture of E,E and E,Z diastereoisomers in good yield.