Switchable Smiles Rearrangement for Enantioselective O-Aryl Amination.

Asymmetric assembly of atropisomeric anilines from abundant and readily available precursors is one of the most challenging but valuable processes in organic synthesis. The use of highly efficient Smiles rearrangement to accomplish switchable enantioselective amination reactions of O-arenes provides access to nonsymmetric 2'-amino[1,1'-binaphthalen]-2-ol (i.e., NOBIN-type) and [1,1'-binaphthalene]-2,2'-diamine (i.e., BINAM-type) derivatives. This transition metal-free strategy provides a powerful way to access a wide range of advanced highly functionalized enantioenriched anilines.