Building with Cubane-1,4-diyl. Synthesis of Aryl-Substituted Cubanes, p-[n]Cubyls, and Cubane-Separated Bis(arenes)
文摘
On treatment with an organolithium 1,4-diiodocubane generates cubane-1,4-diyl, a highly reactivespecies, shown here to be a versatile precursor to numerous aryl substituted cubanes, available now for thefirst time in high yield. The diyl is demonstrated to provide a good route to bicubyl and its derivatives. A kindof "living polymerization" of the diyl is developed to give the p-[n]cubyls. These oligomers are rigid rodsmade up of cubanes linked together at the 1 and 4 positions, each cubane adding ~4.15 Å to the length. Theproperties of these rods, some more than 15 Å long, are discussed, as are methods for modifying their solubility.X-ray crystallographic analyses of some of these compounds are presented, with emphasis on packing parameters.