The invention relates to a process for the manufacture of bidentate ligands of the formula IA and IIA, characterized in that N,N-(optionally substituted) dialkylamino phosphines bound to an aromatic carbon are lithiated in ortho-position and the lithiated compounds are further converted to said bidentate ligands: wherein X₁ is NR, O or S; X₂ is CHR₁ or CR₁; X₃ is CHR₂ or NR₂ or, if X₂ is CR₁, X₃ is CR₂ or N; and R, R₁ and R₂ are radicals such as alkyl groups or R₁ and R₂ together form an annealed ring; Y₁*, Y₂* and Y₁'* are, independently of each other, an element of the fifth group of the periodic table of elements as such or in thioxo or oxo form; Z₁*, Z₂*, Z₃*, Z₄*, Z₁'*, Z₂'* are, independently of each other, for example halogen, hydrogen, or an unsubstituted or substituted moiety selected from radicals such as alkyl groups; the substituents have otherwise the meanings given in the specification; and the ligands are capable of forming metal complexes, which can be used as catalysts in stereoselective synthesis, especially hydrogenation, of various organic molecules.