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Publication 164
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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.