Synthesis of Symmetrical Polynitrohelicenes and Their Chiral Recognition in the Charge Transfer Complexation

Derivatives of optically active 1,12-dimethylbenzo[c]phenanthrene-5,8-dicarboxylic acid can be nitrated regioselectively, giving symmetrically polyfunctionalized helicenes. The dicarboxylic acid or its dimethyl ester is dinitrated with fuming nitric acid in acetic acid at the 4,9-positions. When the reaction is conducted in fuming nitric acid, a 2,4,9,11-tetranitrohelicene is obtained. Analogously, 1,12-dimethylbenzo[c]phenanthrene-5,8-dinitrile gives 2,11-dinitro- or 4,9-dinitrohelicene depending on the conditions, and the former compound is converted to a 2,4,9,11-tetranitrohelicene. The tetranitrohelicenes form charge-transfer (CT) complexes with an electron-rich chiral diaminohelicene in solution. The studies on the chiral recognition reveal that the combinations of the same configuration of the helicenes form more stable complexes than that of the enantiomeric helicenes.