The Aryl‐Pyrrolidine‐tert‐Leucine Motif as a New Privileged Chiral Scaffold: The Role of Noncovalent Stabilizing Interactions

Privileged chiral scaffolds – structures that have been demonstrated to induce high levels of enantioselectivity across a variety of mechanistically distinct reactions – have proven profoundly enabling to the discovery of new asymmetric catalytic reactions. This chapter outlines the development of dual H-bond donors (HBDs) bearing aryl-pyrrolidino- tert -leucine motifs as a new member of this select class of chiral compounds. These HBD catalysts have proven broadly useful in a variety of CC and Cheteroatom bond-forming processes, with enantioselectivity dictated primarily through selective stabilizing noncovalent interactions. Three detailed case studies on the mechanism of enantioinduction with aryl-pyrrolidino- tert -leucine HBDs are discussed, highlighting the cooperative features of these simple organic molecules that are likely responsible for the privileged nature of this scaffold.