Controlling Selectivity by Controlling the Path of Trajectories. Academic Article uri icon


  • Consideration of the role of dynamic trajectories in [1,2]- and [2,3]-sigmatropic rearrangements suggests a counterintuitive approach to controlling the selectivity. In our hypothesis, [2,3] selectivity can be promoted by reaction conditions that thermodynamically disfavor the [2,3] rearrangement step and thereby make the transition state later. The application of this idea has led to a successful prescription for dictating the selectivity in Stevens/Sommelet-Hauser rearrangements of ammonium ylides. A combination of kinetic isotope effects, crossover experiments, and computational dynamic trajectories support the idea that the selectivity is controlled through control of the path of trajectories.

altmetric score

  • 14.6

author list (cited authors)

  • Biswas, B., & Singleton, D. A

citation count

  • 42

complete list of authors

  • Biswas, Bibaswan||Singleton, Daniel A

publication date

  • January 2015