Previously we have reported the first chiral spiro bis(isoxazoline) ligands (SPRIXs) bearing a chiral spiro skeleton and two isoxazoline rings, and demonstrated the first example of Pd-catalyzed enantioselective aminocarbonylation of alkenylamide. In order to achieve the highly catalytic enantioselective aminocarbonylation, the effects of substituents on the isoxazoline rings of SPRIX and anions for Pd salts on the reaction were investigated. Among the combination we examined, the Pd-complex prepared from [Pd(CH3CN)4](BF4)2 and (M,S,S)-i-Pr-SPRIX in the ratio of 1 to 2 showed highest catalytic activity. In particular the reaction of alkenylurea afforded nitrogen-containing bicyclic product in good chemical yield with up to 86% ee. The X-ray crystallographic analysis of the Pd-SPRIX complex indicated the structure composed of one Pd metal, two molecular of (M,S,S)-i-Pr-SPRIX and two BF4 anions.
