(+)-(R,Z)-5-Muscenone and (-)-(R)-muscone by enantioselective aldol reaction and Grob fragmentation.

(+)-(R,Z)-5-Muscenone ((R)-1) was synthesized by an enantioselective aldol reaction, catalyzed by new ephedrine-type Ti reagents (up to 70 % enantiomeric excess). Substrate-directed diastereoselective reduction of the aldol product and Grob fragmentation of the tosylate of the resultant 1,3-diol afforded (+)-1. This approach also gave access to (-)-(R,E)-5-muscenone and (-)-(R)-muscone.

Tandem asymmetric conjugate addition--silylation of enantiomerically enriched zinc enolates. Synthetic importance and mechanistic implications.

[formula: see text] The zinc enolates, resulting from the copper-catalyzed enantioselective conjugate addition of dialkyl zinc reagents to cyclic and acyclic enones, could be trapped, quantitatively, as silyl enol ethers with TMSOTf in apolar solvents or with TMSCI and NEt3. These enantiomerically enriched silyl enol ethers were submitted to four synthetic transformations to show their synthetic utility. The zinc enolates obtained from acyclic enones were found to be configurationally stable, as shown by the stereochemistry of the silyl enol ethers.