Enantioselective Synthesis, Crystal Structures, and Stereoisomerism of Substituted ,,,-Tetraphenylenes.

We have achieved the enantioselective synthesis of highly strained, substituted ,,,-tetraphenylenes (≤98% ee) via the cationic Rh(I)/()-H-BINAP complex-catalyzed chemo-, regio-, and enantioselective intermolecular cross-[2+2+2] cycloaddition of teraryl diynes with dimethyl acetylenedicarboxylate. X-ray crystallographic analyses demonstrate the highly bent structures of the -substituted benzene moieties, and density functional theory calculations reveal the large local strain of the paraphenylene unit. H nuclear magnetic resonance analyses and theoretical calculations elucidate the stereoisomerism, indicating that the nonrotatable -disubstituted biphenyl structure results in and isomers.