| A new concept for nucleophilic catalysis has been developed and this strategy was successfully applied to the kinetic resolution of benzylic amines and propargylic amines. The first catalytic enantioselective desymmetrization of meso-1,2-diarylaminoethanes has been introduced. A combination of nucleophilic catalyst DMAP and hydrogen bonding catalyst afforded the monoacylated products in good yields and good to excellent enantioselectivity. A catalytic enantioselective Steglich rearrangement reaction has also been developed using our dual catalytic approach for nucleophilic catalysis. A novel catalytic enantioselective transformation between azlactones and isoquinolines has been developed. To the best of our knowledge, this type of functionalization of isoquinolines with azlactones is unprecedented.;A redox neutral reaction cascade that involves the functionalization of the relatively unactivated C–H bond α to the nitrogen of cyclic amines has been developed. This transformation represents a fast route to synthetically useful aminal building blocks. A mechanistically unique 2,3-annulation of indole based on the tert-amino effect 1,5-hydride shift/ring closure sequence has been shown. This redox-neutral C–H functionalization leads to a new class of ring fused indolobenzazepines and features short reaction times. Apart from indole, the substrate scope includes pyrroles and 1,2-diarylhydrazines. |
