Cope rearrangement degeneration

The Cope rearrangement of hexa-l,5-diene does not allow for differentiation of starting material and product this is called a degenerate Cope rearrangement. Another example is the automerization of bicyclo[5,l,0]octa-2,5-diene 7 ... 

It was pointed out earlier that a Cope rearrangement of 1,5-hexadiene gives 1,5-hexadiene. This is a degenerate Cope rearrangement (p. 1380). Another molecule that undergoes it is bicyclo[5.1.0]octadiene (105). At room temperature the NMR... 

Another compound for which degenerate Cope rearrangements result in equivalence for all the carbons is hypostrophene W1). In the case of the compound barbaralane (108) (bullvalene in which one CH=CH has been replaced by a CH2) ... 

Consider the two examples of degenerate Cope rearrangement shown in Fig. 19. 

SCHEME 18. van der Waals volume of activation AV and volume of activation calculated for degenerate Cope rearrangement of 1,5-hexadiene... 

This is perhaps the area where there is the most optimism of attaining the elusive goal of neutral homoaromaticity. It has been suggested that semibullvalene [83], which undergoes degenerate Cope rearrangements through a homoaromatic transition state [83b] (2) with extremely low... 

Fivefold degenerate reversible [3,3]-sigmatropic shifts were first reported in 1988116,117 in the CPD-amidine system 257, where AG g = 117 to 120 kJmol-1 (equation 88) (for aza-Cope rearrangements see Section IV.E.2). In addition, a slow accumulation of a colored by-product was observed at elevated temperatures. This was identified as a product of a novel intramolecular carbon to nitrogen 1,4-shift of the methoxycarbonyl... 

Interesting examples of a tandem Cope-Cope rearrangement are represented by the transformation of Cookson s diester 499, which proceeds thermally to afford its ring-degenerate isomer 500 (330-350 °C, as a melt) (equation 188)246, and by thermal isomerization of bicyclic triene 501 into hexahydro-1-vinylnaphthalene 502 upon heating in chlorobenzene at 220 °C for 20 h (equation 189)247. 

Characteristics and energetics of the photo-induced electron-transfer degenerate Cope rearrangement of 2,5-diarylhexa-l,5-dienes have been reported in detail. Oxygentrapping experiments have established the two-step nature of the rearrangement of... 

When the dibromo dicyano derivative 368 was later prepared, it was found to exhibit a higher activation barrier to degenerate Cope rearrangement than the parent hydrocarbon... 

Figure 12.6. a) Cope rearrangement of 1,5-hexadiene (6) oxy-Cope rearrangement (c) divinyl-cyclopropane rearrangement (d) degenerate rearrangements of bullvalene. 

Doering and Roth, at the time of their first investigations of 86 in 1963, proposed that the structure 90, which they named bullvalene, should undergo degenerate Cope rearrangements that would make each of the ten CH groups equivalent.179 Equation 12.109 illustrates just a few of these transformations.180... 

---