PHOTOINDUCED MOLECULAR-TRANSFORMATIONS .19. PHOTOCHEMICAL NITROGEN INSERTION INTO BICYCLO[2.2.1]HEPTANONES - THE PHOTOCHEMISTRY OF OXIMES OF (+)-FENCHONE AND (+)-CAMPHOR

The photolysis of the oxime of (+)-fenchone in methanol gave a 1:1 ratio of two isomeric lactams, 1,4,4-trimethyl-2-azabicyclo[3.2.1]octan-3-one (13%) and its previously undescribed isomer, 1,4,4-trimethyl-3-azabicyclo[3.2.1]octan-2-one (13%), with the accompanying formation of alkenoic acid amides (10%). Photolysis of the oxime of (+)-camphor in methanol similarly gave two isomeric lactams, 1,8,8-trimethyl-2-azabicyclo[3.2.1]octan-3-one (alpha-camphidone) (12%) and 1,8,8-trimethyl-3-azabicyclo[3.2.1]octan-2-one (12%), in a 1:1 ratio, as well as an alkenoic acid amide (alpha-campholenic amide) (32%). Nitriles arising from photochemical alpha-fission were obtained, in 11 and 6% yield, through photolysis of the respective oximes. Therefore, methyl groups attached to the alpha-carbons had little affect on the direction of the photoreaction of bicyclo[2.2.1]heptanone oxime. 2- and 3-Azabicyclo[3.2.1]octanones can thus be synthesized by the photoreaction of bicyclo[2.2.1]heptanone oximes, which can be carried out without the use of any other reagent.