Journal
CHEMICAL SCIENCE
Volume 14, Issue 15, Pages 3963-3972Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/d3sc00571b
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This study reports the enantio- and/or diastereoselective synthesis of planar chiral polycyclic aromatic hydrocarbon (PAH)-based [2.2]cyclophanes via base-mediated intermolecular macrocyclization and Rh- or Ni-catalyzed intramolecular double [2 + 2 + 2] cycloadditions. DFT calculations reveal that the diastereoselectivity is kinetically determined by the second [2 + 2 + 2] cycloaddition. Single crystal X-ray diffraction analyses confirm the repulsion between the facing triphenylene or [5]helicene skeletons, leading to curved structures with bulged centers.
Planar chiral [2.2]cyclophanes with two aromatic rings in close proximity have attracted much attention for their applications as chiral materials and catalysts because of their stable chirality and transannular interactions. Although numerous [2.2]cyclophanes have been synthesized to date, only a few polycyclic aromatic hydrocarbon (PAH)-based ones have been reported, and the simultaneous control of two planar chiralities of the two aromatic rings facing each other has not been achieved. Here we report the enantio- and/or diastereoselective synthesis of planar chiral PAH-based [2.2]cyclophanes ([2.2]triphenylenophanes) via the high-yielding base-mediated intermolecular macrocyclization and Rh- or Ni-catalyzed intramolecular double [2 + 2 + 2] cycloadditions. DFT calculations have revealed that the second [2 + 2 + 2] cycloaddition kinetically determines the diastereoselectivity. Single crystal X-ray diffraction analyses have confirmed that the facing triphenylene or [5]helicene skeletons strongly repel each other, resulting in curved structures with bulged centers.
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