164. P. Müller, G. Bernardinelli, P. Nury,
     “Synthesis of bicyclo[3.2.2]nonadienones via enantioselective cyclopropanation of racemic cyclohexen-3-yl diazoacetate”
     Tetrahedron: Asymmetry 2002, 13, 551-558.

Optically active (1S,5R)-(+)-3-azabicyclo[3.2.2]non-6-en-2-one (+)-7 was synthesized via enantioselective intramolecular cyclopropanation of racemic cyclohexen-3-yl diazoacetate 10 in the presence of [Rh₂({(2S)-meox}₄] catalyst. The cyclopropanation product (−)-9 was converted to the azide 8, which underwent successive Curtius and 3-aza-Cope rearrangements to afford 18, which was reduced to the bicyclic azepinone (+)-7. An analogous sequence based on Cope rearrangement of the SEM-protected enol ether 20 afforded (1S,5R)-bicyclo[3.2.2]nona-3,6-dien-2-one 22.

DOI : 10.1016/S0957-4166(02)00105-2