Synthesis of 1,4-Annulated Cyclooctatetraenophanes Based on a Novel Cubane Building Block Approach

A general synthetic approach to strained 1,4-annulated cyclooctatetraene-based cyclophanes is described. A key feature in this approach is exploitation of the cubane core as a masked cyclooctatetraene synthon. Thus, 1,4-disubstituted cubanes 3 and 4 used as precursors to cyclooctatetraenophanes have been prepared in four steps from the readily available 1,4-cubanedicarboxaldehyde (5). The synthesis of 3 was effected by palladium/copper-mediated coupling of 1,4-bis[(Z,Z)-2-iodovinyl]cubane (6) and 1,4-bis[(Z,Z)-but-1-en-3-ynyl]cubane (8). For the synthesis of 4, on the other hand, modified Eglington-Glaser coupling was applied for the macrocyclization step. The general characteristic of Rh(I) to induce [2 + 2] cycloreversion of the cubane core to syn-tricyclo[4.2.0.0(2,5)]octa-3,7-diene followed by thermal rearrangement to cyclooctatetraene was applied as a key structural transformation toward targeted cyclooctatetraenophanes 1 and 2.