The first highly enantioselective aminocatalytic activation of α-substituted α,β-unsaturated aldehydes is presented. The chiral primary amine 1 selectively activates α-branched enals toward a well-defined iminium ion/enamine reaction sequence for both Friedel-Crafts/amination and sulfa-Michael/amination cascades. The valuable multifunctional products, having two contiguous sterocenters, are isolated in high enantiomeric purity.
![Asymmetric organocatalytic cascade reactions with ?-substituted ?,?-unsaturated aldehydes](https://www.iciq.org/wp-content/uploads/2014/03/Asymmetric-organocatalytic_7892.gif)