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

We have achieved the enantioselective synthesis of highly strained, substituted o , m , o , p -tetraphenylenes (≤98% ee) via the cationic Rh(I)/( R )-H 8 -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 para -substituted benzene moieties, and density functional theory calculations reveal the large local strain of the paraphenylene unit. 1 H nuclear magnetic resonance analyses and theoretical calculations elucidate the stereoisomerism, indicating that the nonrotatable ortho -disubstituted biphenyl structure results in cis and trans isomers.