Construction of Cyclic Sulfamidates Bearing Two <i>gem</i>-Diaryl Stereocenters through a Rhodium-Catalyzed Stepwise Asymmetric Arylation Protocol

A rhodium-catalyzed stepwise asymmetric 1,4- and 1,2-addition of arylboronic acids to α,β-unsaturated cyclic N-sulfonyl ketimines has been developed, providing a wide range of gem-diaryl-substituted chiral benzosulfamidates with high optical purities. C1-Symmetric chiral diene and branched chiral sulfur–olefin ligands were sequentially utilized in this double-arylation process for high stereocontrol. Further synthetic utility offers new opportunities for the facile construction of otherwise difficult to access polycyclic heterocycles.