Synthesis of N-doped chiral macrocycles by regioselective palladium-catalyzed arylation

A series of nitrogen (N)-doped macrocycles was successfully synthesized through palladium-catalyzed arylation. X-ray crystallographic characterization revealed the formation of isomeric products depending on the substituents on the N atoms. Notably, two intrinsically chiral macrocycles <b>MC1</b> and <b>MC3</b> with <i>C</i> ₁ symmetry were successfully obtained. These macrocycles exhibit exceptional photophysical properties, particularly remarkable high fluorescence quantum yields (Φ_F up to 0.69). Furthermore, enantiomeric resolution of inherent chiral <b>MC1</b> was achieved using preparative chiral HPLC, enabling detailed investigation of its chiroptical behavior through circular dichroism and circularly polarized luminescence spectroscopy.