Chemistry and Structure of Phenylcubanes

Article abstract of DOI:10.1021/jo00289a007

Phenylcubanes show unusual reactivity toward metalation and oxidation.Metalation of 1,4-bis((diisopropylamino)carbonyl)-2,7-diphenylcubane, 1, occurs at the cubane skeleton while oxidation of 1,4-bis((diisopropylamino)methyl)-2,7-diphenylcubane, 7, resulted in the formation of benzoic acid.The X-ray structure of 7 shows a short phenyl-cubane bond length of 1.484 Angstroem, and the C1-C2 bond, the cubane bond between the two substituents, is substantially longer than in an unsubstituted cubane (1.607 vs. 1.558 Angstroem).The selective functionalization of either the phenyl or the cubane moiety and the synthesis of 1,4-diphenylcubane-2,7-dicarboxylic acid, 8, via oxidation of the (diisopropylamino)methyl group under mild conditions, were achieved.