Unusual reactivity of bent acenes: reactions of [6](1,4)naphthalenophane and [6](1,4)anthracenophane with electrophiles

The unusual reactivity of [6](1,4)naphthalenophane (2) and [6](1,4)anthracenophane (3), the smallest-bridged acenophanes hitherto known, in electrophilic reactions has been disclosed. These reactions include (i) acid-catalyzed telomerization, (ii) peracid oxidation, and (iii) addition with dienophiles. Semi-empirical molecular orbital calculations (MNDO and MNDO/PM3) were performed in order to compare the geometries, energies, and bonding characters of 2 and 3 with those of [6]paracyclophane (1)