Axially chiral biaryl compounds are prepared by coupling reactions, e.g., Ullmann coupling, Suzuki–Miyaura reaction, or palladium-catalyzed arylation of arenes. Subsequent to the synthesis, the racemic biaryl is resolved by classical methods. Diastereoselective coupling can be achieved through the use of a chiral bridge that links the two aryl groups or through the use of a chiral auxiliary at one of the positions proximal to axial bridge. Enantioselective coupling can be achieved through the use of a chiral leaving group on one of the biaryls or under oxidative conditions that utilize chiral amines to set the axial configuration. 
Individual atropisomers can be isolated by seed-directed crystallization of racemates. Thus, 1,1'-Binaphthyl crystallizes from the melt as individual enantiomers.