Chemistry of adamantane. Part XI 1,2-Disubstituted adamantanes. Synthesis and reactions of adamantano[2,1-b]- and protoadamantano-[4,5-b] [1,5]benzodiazepines


  • Part X. J. K. Chakrabarti, T. M. Hotten, S. Sutton and D. E. Tupper, J. Med. Chem., 19, 967 (1976).


The synthesis and reactions of adamantano[2,1-b]-and protoadamantano[4,5-b] [ 1,5]benzo-diazepines are described. 12,13-Dihydro-1 1aH-protoadamantano[4,5-b ] [ 1,5]benzodiazepin-12-one (15) rearranged to 2,3-dihydro-l-(protoadamant-4-en-4-yl)benzimidazol-2-one (22). This rearrangement does not proceed with 2-fluoro-5,5a,12,13-tetrahydroadamantano[2,1-b][ 1,5]-benzodiazepin-12-one (2c) under similar conditions due to its inability to form an olefinic bond at C5a. A convenient method for the α-carboxylation of ketones using lithium düsopropylamide is also described.