A series of novel meso-(8-substituted naphth-1-yl) porphyrins has been synthesized creating derivatives with a tight recognition environment above the porphyrin plane. The selective synthesis of single atropisomers is discussed. Condensation of bisnaphthaldehyde 12 with phenyldipyrromethane unexpectedly led to selective synthesis of the α, α-5, 10-bridged isomer 14. A mechanism is proposed for this unusual scrambling, and alternative ...