Enantioselective Synthesis of Both Enantiomers of Methyl Dihydrojasmonate Using Solid−Liquid Asymmetric Phase-Transfer Catalysis

Both enantiomers of methyl dihydrojasmonate (−)-1 and (+)-1 were obtained by a short route using asymmetric Michael addition of dimethyl malonate onto pentyl enone 3, followed by nonracemizing demethoxycarbonylation. The key enantioselective step involves a new system of asymmetric solid−liquid phase-transfer catalysis using solvent-free conditions. Enantiomeric excess as high as 90% (91% yield) was achieved.