London Dispersion Favors Cis Selectivity in the Johnson–Corey–Chaykovsky Epoxidation
Abstract
selectivity of the Johnson-Corey-Chaykovsky epoxidation, focusing on bulky alkyl groups as well as halides as dispersion energy donors. Whereas the generally accepted explanation of the observed diastereoselectivity solely invokes steric repulsion, we determined that London dispersion interactions are an important source of stabilization of the preferred transition structures. This was brought forth experimentally by utilizing a series of NMR measurements, double mutant cycles, and crossover experiments. Additionally, density functional theory computations and symmetry-adapted perturbation theory computations were used to determine and quantify the role of noncovalent interactions.
Fields of Study & Subjects
Molecular spectroscopy and chirality
Origins and Evolution of Life
Advanced Chemical Physics Studies
Publication details
- Journal / source
- The Journal of Organic Chemistry
- Publisher
- American Chemical Society (ACS)
- Volume
- 91
- Issue
- 14
- Pages
- 4829–4841
- Publication date
- 26 March 2026
- Language
- EN