Palladium- and Brønsted acid-catalyzed enantio-, site- and E/Z-selective addition of alkylidenecyclopropanes with imines.

Transition-metal catalyzed functionalization of ACPs has been widely investigated in cycloaddition and 1,3-difunctionalization reactions. However, the transition metal catalyzed nucleophilic reactions of ACPs have rarely been reported. In this article, an enantio-, site- and E/Z-selective addition of ACPs with imines for the synthesis of dienyl substituted amines has been developed via palladium- and Brønsted acid co-catalysis. A range of synthetically valuable dienyl substituted amines were effectively prepared with good to excellent yields and excellent enantio- and E/Z-selectivities.

Palladium-Catalyzed Nucleophilic Reaction of Alkylidenecyclopropanes with ß,γ-Unsaturated α-Ketoesters: Ligand-Controlled Divergent Synthesis.

A palladium-catalyzed ligand-controlled selective 1,4-addition and cycloaddition reaction of ß,γ-unsaturated α-ketoesters with alkylidenecyclopropanes (ACPs) has been developed. Using ACPs and ß,γ-unsaturated α-ketoesters as starting materials, γ-dienyl-α-ketoesters and dihydro-2H-pyrans could be prepared selectively by modulating the ligand. A range of multisubstituted α-ketoesters and dihydro-2H-pyrans were obtained in moderate to excellent yields with excellent regioselectivities.