A modular way towards biaryls: Highly enantioenriched biphenyls can be prepared based on a transition-metal-free aryl-aryl coupling followed by efficient desymmetrization or deracemization and chemoselective functionalization (see scheme).

A new aryne-mediated tandem cross-coupling/P-cyclization sequence starting from tertiary phosphine-boranes and 1,2-dibromobenzenes is reported. P-chirogenic dibenzophospholes become accessible in a regio-, chemo-, and diastereoselective way.