Deeper Insight into the Mechanism of the Reaction of Photogenerated Metallaketenes and Imines

Abstract

The reaction mechanism between Fischer carbene complexes and imines to produce beta-lactams has been studied by a combination of computational (DFT) and experimental methodologies. After the photogeneration of metalla-cyclopropanone species, the reaction initiates by 1,3-migration of the metal fragment from the former carbene carbon atom to the oxygen in the S o hypersurface. In spite of the endothermic nature of this rearrangement, it is biased by the more favorable HOMO(imine)-LUMO+1 interaction in the oxygen-coordinated ketene. This species reacts with the imine to yield metalla-zwitterions, which form the final products through a four electron conrotatory ring closure. The presence of the metal moiety during the whole reaction coordinate is demonstrated by the use of a chiral chromium(0) alkoxycarbene complex, which produces low but significant ee in the reaction with imines. The cis-trans stereoselection derives from the nucleophilic addition of the nitrogen atom of the imine to the oxygen-coordinated ketene, since there are no significant differences between the classical and the metallated processes in the electrocyclation step leading to the final 2-azetidinones.