The lithiation of 2,7-dihydrodinaphthoheteroepines (5) with 2.2equiv of lithium naphthalenide in THF at −78°C gives dianionic intermediates 8, which by reaction with different electrophiles [H 2 O, D 2 O, t BuCHO, Me 2 CO, Et 2 CO, (CH 2 ) 4 CO, (CH 2 ) 5 CO] at the same temperature, followed by hydrolysis, leads to unsymmetrically 2,2′-disubstituted binaphthyls 6. When the lithiation is performed with an excess of lithium in the presence of a catalytic amount of 4,4′-di-tert-butylbiphenyl (DTBB, 10mol%), a double reductive cleavage takes place to give dianionic intermediate 9, which by reaction with different electrophiles [H 2 O, Me 2 CO, Et 2 CO, (CH 2 ) 4 CO, (CH 2 ) 5 CO], followed by hydrolysis with water, yields symmetrically 2,2′-disubstituted binaphthyls 7. In the case of starting from (R)-5a, the reductive opening by treatment with 2.2equiv of lithium naphthalenide followed by reaction with H 2 O or (CH 2 ) 5 CO as electrophiles and final hydrolysis, leads to enantiomerically pure compounds (R)-6aa and (R)-6af, respectively.