Synthesis of Cyclophenacene‐ and Chiral‐Type Cyclophenylene‐Naphthylene Belts

Abstract We report the synthesis of a [20]cyclophenacene‐type cyclophenylene‐naphthylene (CPN) belt and enantioselective chiral‐type CPN belts (up to >99 % ee ) by cationic rhodium(I)‐catalyzed intramolecular [2+2+2] cycloaddition naphthalene‐embedded cyclic polyynes. The depth‐expanded was also attempted, but final unsuccessful. Theoretical calculations clarified that reactivity depends on stability transition state in initial oxidative step which is subject molecular strain. cylindrical structures these were confirmed X‐ray crystallographic analyses. As result π‐extension through introduction naphthalenes belts, anisotropy dissymmetry factors electronic circular dichroism circularly polarized luminescence are amplified compared with corresponding zigzag‐type chiral cyclophenylene belts.