Acetylketene (1) was generated by flash pyrolysis of 2,2,6-trimethyl-4H-1,3-dioxin-4-one (6). The selectivities of 1 toward a number of representative functional groups were measured for the first time in a series of competitive trapping reactions. The trend in reactivities toward 1 follows the general order amines > alcohols >> aldehydes approximately ketones and can be rationalized by considering both the nucleophilicity and the electrophilicity of the reacting species. Alcohols show significant selectivity based on steric hindrance, with MeOH approximately 1 degrees > 2 degrees > 3 degrees. These selectivities are consistent with the activation energies and the pseudopericyclic transition structure previously calculated for the addition of water to formylketene. The results, presented here, of ab initio transition structure calculations for the addition of ammonia to formylketene are qualitatively consistent with the experimental trends as well. N-Propylacetacetimidoylketene (2) was generated by the solution pyrolysis of tert-butyl N-propyl-3-amino-2-butenoate (9a) and showed similar selectivity toward alcohols as opposed to ketones and similar steric discrimination toward alcohols. This is again in agreement with previous ab initio calculations. Taken together, these experimental trends in the reactivities of both 1 and 2 toward a variety of reagents provide strong, although indirect support for the planar, pseudopericyclic transition structures for these reactions which are predicted by ab initio calculations.

Allowed by orbital symmetry rules, the [3,5] sigmatropic ester rearrangement of ester 1 even has a lower barrier than a competing [3,3] rearrangement, according to ab initio calculations. This surprising result is a consequence of the lack of orbital overlap in the pseudopericyclic transition state.

Multiphoton infrared absorption from a focused, pulsed CO(2) laser was used to initiate gas-phase thermal reactions of cis- and trans-3-penten-2-yl acetate. By varying the helium buffer gas pressure, it was possible to deduce the product distribution from the initial unimolecular reactions, separate from secondary reactions in a thermal cascade. Thus, trans-3-penten-2-yl acetate gives 54 +/- 5% of beta-elimination to give trans-1,3-pentadiene, 40 +/- 3% of [3,3]-sigmatropic rearrangement to give cis-3-penten-2-yl acetate and 6 +/- 4% of cis-1,3-pentadiene. Similar irradiation of cis-3-penten-2-yl acetate gives 45 +/- 1% of beta-elimination to give cis-1,3-pentadiene, 32 +/- 2% of [3,3]-sigmatropic rearrangement to give trans-3-penten-2-yl acetate and 23 +/- 2% of trans-1,3-pentadiene. The latter process is an eight-centered delta-elimination, which is argued to be a pseudopericyclic reaction. Although beta-eliminations have been suggested to be pericyclic, B3LYP/6-31G(d,p), MP2 and MP4 calculations suggest that both beta- and delta-eliminations, as well as [3,3]-sigmatropic rearrangements of esters are primarily pseudopericyclic in character, as judged by both geometrical, energetic and transition state aromaticity (NICS) criteria. Small distortions from the ideal pseudopericyclic geometries are argued to reflect small pericyclic contributions. It is further argued that when both pericyclic and pseudopericyclic orbital topologies are allowed and geometrically feasible, the calculated transition state may be the result of proportional mixing of the two states; this offers an explanation of the range of pseudopericyclic and pericyclic characters found in related reactions.

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