Synthesis of bicyclo[4.n.1]alkanones.
Cyclic beta-keto ester monoanions react with 1,4-dihalobutenes to give C-alkylated products which subsequently undergo a stereoselective SN2' O-alkylation reaction to yield functionalized enol ethers. When the starting material was ethyl cyclopentanone carboxylate, the C-alkylated product, treated with a base, directly afforded the functionalized bicyclo[4.2.1]nonanone. The enol ethers were submitted to a flash vacuum thermolysis (FVT) reaction to readily afford functionalized bicyclo[4.n.1]alkanones (n = 3, 4). This reaction sequence was applied to the synthesis of a functionalized tricyclo[7.4.1.0(1,5)]tetradecanone, which represents an analogue to the tricyclic core of ingenol.
Montalt
Joaquin
J
Laboratoire de Chimie Organique Synthétique associé au CNRS (UMR 7123), Faculté de Chimie, Université Louis Pasteur, 1, rue Blaise Pascal BP, 296/R8, F-67008 Strasbourg Cedex, France.
Linker
Frédéric
F
Ratel
Frédéric
F
Miesch
Michel
M