Enantioselective Allylation of (2E,4E)-2,4-Dimethylhexadienal: Synthesis of (5R,6S)-(+)-Pteroenone

Abstract

Allylation, trans- and cis-crotylation of (2E,4E)-2,4-dimethylhexadienal, a representative alpha,beta,gamma,delta-unsaturated aldehyde, was carried out under different catalytic and stoichiometric conditions. The reactions catalyzed by organocatalysts TRIP-PA and N,N'-dioxides gave the best results with respect to yields, asymmetric induction, and catalyst load in comparison to other procedures.

The developed methodology was applied in the enantioselective synthesis of (5R,6S)-(+)-pteroenone, a defensive metabolite (ichthyodeterrent) of the Antarctic pteropod Clione antarctica.

Keywords

• aldehyde
• allylation
• asymmetric synthesis
• Bronsted acid
• Lewis base