Homochiral ligands (R,R)- 2 , (R,R)- 3a , (R,R)- 3b , (S,S)- 4a , and (S,S)- 4b were prepared form cis-1-phenylcyclohexane-1,2-diol or cis-2-phenylcyclohexanol and were tested as ligands for the nucleophilic addition of alkyllithiums to benzaldehyde 4-anisidineimine. While moderate enantioselectivities (up to 43% e.e.) were observed with (R,R)- 3b and (S,S)- 4a , (R,R)- 2 and (R,R)- 3a did not show enantioselectivities. Homochiral secondary amines (S,S)- 6a and (S,S)- 6b were also prepared from cis-2-azido-2-phenylcyclohexanol. Moderate enantioselectivities (up to 50%) were observed when they were used as chiral lithium amide base precursors for the deprotonation of 4- t-butylclohexanone.