An efficient catalytic asymmetric ring-opening reaction of donor–acceptor cyclopropanes with primary arylamines was developed. The reaction was achieved through the utilization of a chiral heterobimetallic catalyst, delivering a variety of chiral γ-amino acid derivatives in up to 93% yield and 99% ee. Stereochemical experiments suggest a dominant role for kinetic resolution in this asymmetric process, which is supported by a computational study of the reaction coordinate. A class of chiral bimetallic Lewis acid catalysts formed through a ligand exchange/transmetalation process was introduced in this work. The symmetric structure of the bimetallic catalyst, i.e., Yb­(OTf)3-Yb­[P]3, was confirmed with X-ray crystallography.

A double divergent process has been developed for the reaction of α-enaminones with quinones through facile manipulation of catalyst and additive, leading to structurally completely different products. The two divergent...

The formation of enamine from primary arylamines was detected and confirmed by nuclear magnetic resonance spectroscopy. The presence of a radical quencher, e.g., (2,2,6,6-tetramethylpiperidin-1-yl)­oxidanyl, was found to be essential for the detection of enamine formation. A direct synthesis of α-enaminones from primary arylamines and ketones was also developed. Mechanistic investigation of α-enaminone formation suggests that an amine radical cation generated through O2 singlet energy transfer was involved in initiating α-enaminone formation. The reactivity and utility of α-enaminones were explored with a [3+3] cycloaddition reaction of enones affording dihydropyridines in good yields (58–85%). α-Enaminones displayed a set of reactivities that is different from that of enamines. The knowledge gained in this work advances our basic understanding of organic chemistry, providing insights and new opportunities in enamine catalysis.