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-dimethylbicyclo2.2.1]heptan-2-ylidenemethyl)-N′-(4-methylphenylsulfonyl)-imidocarbamate as a 3: 1 mixture of E,E and E,Z diastereoisomers in good yield. Published in Russian in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 10, pp. 1495–1500. The text was submitted by the authors in English.