Enantio‐ and Diastereoselective Synthesis and Spiral‐Stair‐Like Single Helix Assembly of Figure‐Eight Cyclophenylenes

Helix assemblies of chiral molecules can transfer microscopic unimolecular chirality to macroscopic supramolecular chirality, enhancing various chiral properties. In addition to the commonly observed spiral-column-like helix assembly, a small number of spiral-stair-like helix assemblies have also been reported in aromatic nanocarbons with multiple chirality-related irregularities. However, they require separation of diastereomers and/or enantiomers or do not have stable chirality. Here, we report the enantio- and diastereoselective synthesis of figure-eight [10]cyclophenylenes with stable helical chirality by the rhodium-catalyzed four consecutive intramolecular [2 + 2 + 2] cycloadditions of dodecaynes with two flexible biphenyl units. The chiral figure-eight [10]cyclophenylene with ethyl and methyl side chains exhibits the spiral-stair-like single helix assembly in the crystal due to CH-π and CH-O interactions and good CPL properties in solution. Experimental verification of the enantio- and diastereodetermining steps of four consecutive [2 + 2 + 2] cycloadditions is also reported.