Peptide-catalyzed consecutive 1,6-and 1,4-additions of thiols to α,β,γ,δ-unsaturated aldehydes

Regio- and enantioselective addition of thiols to alpha,beta,gamma,delta-unsaturated aldehydes was performed with a resin-supported peptide catalyst. It was shown that a 1,4-adduct was generated mainly at the initial stage of the reaction, and this was eventually converted to a thermodynamically stable 1,6- and 1,4-diadduct through retro-addition/addition reactions.