THE MECHANISM OF THE OLEFIN-TO-CARBENE REARRANGEMENT FOR 9-PHENYL-1(9)-HOMOCUBENE

Two distinct mechanistic pathways exist for the olefin-to-carbene rearrangement of 9-phenyl-l(9)-homocubene to l-phenyl-9-homocubylidene: a phenyl shift or a skeletal carbon-carbon bond shift. Cubane 13C carboxylic acid was prepared and converted to cubyl phenyl 13C ketone and its tosylhydrazone. Determination of the distribution of label in the ethers formed on decomposition of the tosylhydrazone in hot ethanolic base showed that the latter mechanism is operating. © 1990, American Chemical Society. All rights reserved.