Syntheses of Acetylenic Oligophenylene Macrocycles Based on a Novel Dewar Benzene Building Block Approach

A general synthetic approach to strained p-phenylene-based acetylenic macrocycles is described. A key feature in this approach is exploitation of Dewar benzene as an angular p-phenylene synthon. Thus, 1,4-acetal-bridged 2,5-dichloro(Dewar benzene) 5, prepared in four steps from dimethyl acetylenedicarboxylate and 1,2-dichloroethylene, is applied as such a building block in the syntheses of strained macrocycles 13 and anti-20. For the synthesis of 13, m-phenylene units are used as spacers and modified Eglington-Glaser coupling is applied for the macrocyclization step. For the synthesis of anti-20, on the other hand, o-phenylene units are used as spacers and Sonogashira coupling is applied for the macrocyclization step. Macrocycles 13 and anti-20 are characterized crystallographically, and their strained nature is reflected mainly in the deviation of the acetylene units from linearity; the C&tbd1;C-C angles range from 168.7(3) degrees to 179.9(3) degrees in 13 and from 168.0(5) degrees to 171.4(4) degrees in anti-20. Macrocycle 13 shows unique conformational property, namely, the p-phenylene units arranged in parallel in the rectangular framework rotate freely about the long axes, as evidenced by the (1)H NMR studies. Macrocycle anti-20 exhibits a Stokes shift of 179 nm, which is exceptionally large for phenylacetylene macrocycles, presumably owing to the characteristic stacking structure.