Stereodivergent synthesis of 1,4-bifunctional compounds by regio- and diastereoselective Pd-catalyzed allylic substitution reaction

Abstract

Highly stereoselective synthesis of 1,4-bifunctional compounds was accomplished via 1,2-asymmetric induction to α-oxyaldehyde and α-oxyketone followed by regio- and diastereoselective Pd-catalyzed allylic substitution reaction. We found that trifluoroacetate is a suitable leaving group for the allylic substitution reaction. Various nucleophiles containing carbon, nitrogen, and sulfur can be applied to the method. Both 1,4- syn- and 1,4- anti-adducts were synthesized with high stereoselectivity by using stereodivergent reduction of the propargyl alcohols followed by allylic substitution reaction.