Open AccessControlling Selectivity by Controlling the Path of Trajectories
Author(s) -
Bibaswan Biswas,
Daniel A. Singleton
Publication year - 2015
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.5b08635
Subject(s) - chemistry , selectivity , path (computing) , kinetic isotope effect , sigmatropic reaction , counterintuitive , crossover , computational chemistry , transition state , stereochemistry , organic chemistry , deuterium , catalysis , atomic physics , quantum mechanics , physics , artificial intelligence , computer science , programming language
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.