title: Controlling Selectivity by Controlling the Path of Trajectories.
abstract: 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.
authors.affiliation: Department of Chemistry, Texas A&M University , College Station, Texas 77842, United States.
authors.forename: Bibaswan
authors.initials: B
authors.lastname: Biswas
authors.affiliation: Department of Chemistry, Texas A&M University , College Station, Texas 77842, United States.
authors.forename: Daniel A
authors.initials: DA
authors.lastname: Singleton
mesh_terms: D006860:Hydrogen Bonding; D007700:Kinetics; D000432:Methanol / Q000737:chemistry; D015394:Molecular Structure; D000644:Quaternary Ammonium Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D013816:Thermodynamics
chemical_list: D000644:Quaternary Ammonium Compounds; D000432:Methanol