Journal of Organic Chemistry
Journal of Organic Chemistry
5 years ago

Dynamic Effects Responsible for High Selectivity in a [3,3] Sigmatropic Rearrangement Featuring a Bispericyclic Transition State

Dynamic Effects Responsible for High Selectivity in a [3,3] Sigmatropic Rearrangement Featuring a Bispericyclic Transition State
Roberto Villar López, Olalla Nieto Faza, Carlos Silva López
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.

Publisher URL: http://dx.doi.org/10.1021/acs.joc.7b00425

DOI: 10.1021/acs.joc.7b00425

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