Rotation-Locked 2,6-Pyrido-allenophanes: Characterization of all Stereoisomers

New 2,6‐disubstituted pyrido‐allenophanes with locked rotation of aromatic spacers were designed and synthesized. The synthesis was accomplished by Pd‐catalyzed C(sp2)–C(sp) Sonogashira cross‐coupling reaction between 1,3‐diethynylallene (DEA) and 2,6‐dibromopyridine followed by an intermolecular ring closure. Because racemic DEA was employed, pyrido‐allenophanes were obtained as mixtures of stereoisomers that were resolved by preparative HPLC. The conformational space of all these diastereoisomers was explored at the CAM‐B3LYP/6‐31+G*//AM1 level of theory. The isomers were characterized through their symmetry properties revealed in NMR, circular dichroism, and chiral stationary‐phase HPLC experiments. X‐ray diffraction was used to assign and to corroborate the configuration of several diastereoisomers. The unexpected encapsulation of two molecules of CHCl3 in the crystal structures shows the potential of these conformationally hampered allenophanes as encapsulating hosts. Chiral macrocycles: New 2,6‐disubstituted pyrido‐allenophanes were designed, synthesized, and fully characterized thanks to the interplay between NMR, circular dichroism, X‐ray diffraction, and theoretical calculations (see figure). The encapsulation of two molecules of chloroform by one of the isomers highlights their potential use as molecular hosts.