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29844432649
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-1). As a second, note that the two cyclohexenes of the first, highly likely concerted, constitutionally Diels-Alder set would have involved the less well stabilized diradicals had they been involved, whereas the not obviously concerted constitutionally Diels-Alder cyclohexene of the second set is derived, as are the two cyclobutanes, from the optimally stabilized racemic and meso diradicals.
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10944272485
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In the case of the [2+2] cycloaddition of 1,1-difluoroallene, there is good evidence that the ratio of products derived from a diradical intermediate can indeed be pressure-dependent. At high pressure the product resulting from ring closure in the diradical intermediate is favored over that resulting from bond rotation followed by ring closure. Dolbier, W. R., Jr.; Weaver, S. L. J. Org. Chem. 1990, 55, 711-715.
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29844450699
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-1, respectively (standard errors!). Recalculation affords somewhat altered values for the energies of activation that emphasize the poorer quality of the data relating to syn-2: anti-2 → syn-2, 31.4 ± 1.1; syn-2 → anti-2, 34.2 ± 8.2; anti-2 → 1 (methylenecyclohexene), 33.0 ± 1.9; syn-2 → 1, 30.3 ± 6.4 (95% confidence level).
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