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Bispericyclic transition states appear when two independent pericyclic transition states merge into one. They are a particular case of the more general ambimodal concept applied to a transition state that connects reactants with two or more products involving reaction path bifurcations through valley-ridge inflections. In the present computational work, the first example of a bifurcating sigmatropic reaction featuring a bispericyclic transition state is reported for a cyclohexane featuring opposing methylene and a vinylidene fragments. Perhalogenation of a C-C bond in this substrate imparts a strong desymmetrization to the bifurcating potential energy surface. These systems undergo the [3,3] sigmatropic rearrangement with high selectivity, with a preferred product that depends on which halogen decorates the C-C bond. We have found that dynamic effects have a paramount role in the selectivity observed for these reactions.

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Villar Lpez, R.; Faza, O. N.; Silva Lpez, C., J. Org. Chem. 2017, 82 (9), 4758-4765Contributed by Steven BacharachReposted from Computational Organic Chemistry with permissionBispericyclic reactions occur when two different pericyclic reactions merge to have...