“Geländer” macrocycles: Synthesis, chirality and racemisation barriers

A new class of axially-chiral o,o′-bridged biphenyls containing etheroxime chains was obtained in good yields by the macrocyclisation reaction of o,o′-diformylbiphenyl dioxime with several ditosylated or dibrominated reagents. In all cases the enantiomers of the compounds were separated by HPLC using a chiral column (Chiralpack IC) and the stability of the enantiomers (barriers of racemisation) was investigated employing chiral HPLC or chiral Dynamic HPLC techniques. A slight influence on the barrier to rotation was noticed when the enantiomerisation was performed in the presence of suitable alkali cations.