Doubly N‑Methylated Porphyrinoids

Chirality-induced aromatic π-electronic macrocycles, porphyrin and corroles, were synthesized through doubly inner N-methylation through multistep and one-pot reactions, respectively. The exact structures of doubly N-methylated porphyrin and corroles were revealed by single-crystal synchrotron X-ray analysis, exhibiting two N-methyl groups located on neighboring pyrrole rings in up/down conformations. These doubly inner N-substitutions of the π-electronic macrocycles induced distorted geometries, resulting in chiroptical properties after optical resolutions.