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Updated: Jun 13, 2025

Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level
Published on: September 26, 2016
Enantioselective Synthesis, Crystal Structures, and Stereoisomerism of Substituted o,m,o,p-Tetraphenylenes
Yuya Kawai1, Tomohiro Oriki1, Yu Sato1
1Department of Chemical Science and Engineering, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo 152-8550, Japan.
Abstract:
We have achieved the enantioselective synthesis of highly strained, substituted o,m,o,p-tetraphenylenes (≤98% ee) via the cationic Rh(I)/(R)-H8-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. 1H nuclear magnetic resonance analyses and theoretical calculations elucidate the stereoisomerism, indicating that the nonrotatable ortho-disubstituted biphenyl structure results in cis and trans isomers.
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