Enantioselective synthesis of tetra-ortho-substituted axially chiral biaryls through rhodium-catalyzed double [2+2+2] cycloaddition

We have established an enantioselective synthesis of both C-2 symmetric and unsymmetric tetra-ortho-substituted axially chiral biaryls through rhodium-catalyzed double [ 2 + 2 + 2] cycloaddition ( up to > 99% ee). This method serves as an attractive new route to enantioenriched tetra-ortho-substituted axially chiral biaryls in view of the one-step access to substrate diynes and tetraynes starting from readily available alkynes.