Formation and thermal rearrangements of some dimers of butadiene and piperylene. Tests of the validity of thermochemical-kinetic arguments for identification of common biradical intermediates

Abstract

The mechanisms of the dimerization of butadiene and piperylene and the thermal rearrangements of the corresponding dimers are investigated by kinetic and stereochemical techniques. Particular attention is given to the question whether, in the Diets-Alder dimerization of the dienes la or lb, intermediates are involved that are common to the 1,3-sigmatropic rearrangements of the corresponding (2 + 2] dimers 3a and 3b. Substituents on the terminal vinyl position of cis-1,2-divinylcyelobutane (Sa) retard the normal stereospecific boat-like Cope rearrangement to 3,4-dimethyl-cis,cis-cycloocta-1,5-diene and permit the detection of a new "nonboat" process, whicp leads to a stereoisomeric pr6duct. The boat-like rate constant declines with increasing terminal cis-methyl sustitution in the series Sa > cTT-8 > cCT-8 > cCC-8. The total range of the effect amounts to a factor of 1.81 X I 05. The trans-1,2-dipropenylcyclobutanes also give Cope rearrangement products, but this reaction occurs exclusively by an indirect mechanism: prior epimerization to the cis isomer followed by Cope rearrangement of the latter. The rearrangement of trans-3,4-dimethyl-cis,trans-cycloocta-1,5-diene (16) to cis-3,4-dimethyl cis,cis-cycloocta-1,5-diene (10), involving overall epimerization at one asymmetric center and geometric isomerization at one olefinic site, proceeds by a two-step mechanism in which cis.-1,2-trans,trans-dipropenylcyclobutane (cTT-8) is an intermediate. The 1,3-sigmatropic rearrangement of (I R,2R)-( + )-trans-1,2-divinylcyclobutane (3a) gives (R)-( + )-4-vinylcyclohexene (2a) with 7. 7% preservation of enantiomeric purity (corrected for competing racemization of 3a). This corresponds to 54% inversion and 46% retention of configuration of the migrant carbon. By attaching stereochemical labels to the terminal vinyl positions as in optically active tTT-9 and tCT-9, the stereochemistry of the 1,3-sigmatropic rearrangement can be subdivided into the four possible pathways (Schemes IX and X), suprafacial inversion, antarafacial retention, suprafacial retention, and antarafacial inversion. In this way, it can be shown that relative rates through these four pathways are, respectively, 50.2, 6.0, 41.1, and 2.7 from tTT-9, and 49.5, 2.8, 46.8, and 0.9 from tCT-9. These results can be fitted by a biradical mechanism, but are more fruitfully interpreted as mainly the outcome of two competing concerted reactions, one allowed (suprafacial inversion) and one forbidden (suprafacial retention). The absence of any substantial antara contribution in the dipropenyl systems rules out a stereorandom biradical intermediate in the tTT-9 and tCT-9 rearrangements and makes it unlikely in the divinyl system 3a. The Diels-Alder dimerization of trans-penta-1,3-diene-trans-J -d ( 4S, Scheme XIV) in both the exo and endo orientations gives exclusively the product of reaction cis-on-the-diene,cis-on-the-dienophile. This is consistent with a concerted [4s + 2s]cycloaddition and rules out common intermediates in the formation of product tT-13 and cT-12 from the two alternative pathways of Diels-Alder dimerization of piperylene and 1,3-sigmatropic rearrangement of tTT-9.