Figure 1. Examples of important chiral α-arylated cyclic amines and approaches for the construction of α-stereocenters.

a, Numerous drug molecules, such as Cialis, CERC-501, and L-733,060, contain non-racemic α-arylated cyclic amines. These structures are ubiquitous throughout biological systems, where the orientation of the α –substituent can have a dramatic effect on the activity of the resulting product. b, Traditional approaches for asymmetric arylation and alkylation of pyrrolidines proceed via α-lithiation to install aryl⁶ and alkyl⁸ substituents. While effective for pyrrolidine substrates, the procedures are far less effective for larger ring systems or those with sensitive functional groups. c, In this work, enantioselective α-C(sp³)–H coupling of amines is carried out in the presence of a chiral phosphate anion, which permits the arylation of a diverse array of aliphatic amines through the use of a thioamide directing group.