Two 13C-labeled isomers of the formal Diels−Alder adduct of acetylmethyloxirene to tetramethyl 1,2,4,5-benzenetetracarboxylate have been synthesized. Flash vacuum thermolysis of these adducts leads to various isotopic isomers of acetylmethylketene, the ratios of which have been determined by NMR. The surprising finding that the principal product comes from methylpyruvoyl carbene rather than its more stable isomer diacetylcarbene is explained by MPWB1K density functional calculations, which show that the reactant probably undergoes a unimolecular rearrangement to a norcaradiene derivative prior to its fragmentation. Coupled-cluster calculations on the methylpyruvoyl carbene show that it is capable of undergoing three unimolecular isomerizations. The fastest is 1,2-acetyl migration to give acetylmethylketene directly. The next is rearrangement via acetylmethyloxirene to diacetylcarbene and thence by Wolff rearrangement to acetylmethylketene. The least-favorable reaction is degenerate rearrangement via 1,3-dimethyl-2-oxabicyclo[1.1.0]butan-4-one (the epoxide of dimethylcyclopropenone). The combined experimental and computational results indicate that Wolff rearrangement of the diacetylcarbene occurs with a 2.5:1 ratio of the methyl groups despite the fact that they are related by a twofold axis of symmetry in the carbene. Preliminary molecular dynamics simulations are consistent with this conclusion. Taken together, the results suggest that the Wolff rearrangement is subject to the same kind of nonstatistical dynamical effects detected for other kinds of thermally generated reactive intermediates.

[reaction: see text] The mechanisms of perphenylbutenyne reactivity are examined through B3LYP and multireference ab initio calculations on model systems. Calculations for the formation of a naphthalene derivative suggest a process similar to that seen previously in the literature. A new mechanism for perphenylbutenyne dimerization to form a semibullvalene derivative is proposed and supported by calculations.