Work

London Dispersion Favors Cis Selectivity in the Johnson–Corey–Chaykovsky Epoxidation

Year: 2026

Type: article

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.

Source: The Journal of Organic Chemistry

DOI: 10.1021/acs.joc.6c00154

Authors: Marvin H. J. Domanski, Lars Rummel, Saskia N. Krug, Heike Hausmann, Ephrath Solel, Peter R. Schreiner

Institutions: Justus-Liebig-Universität Gießen, University of Edinburgh

Language: English

Topic: Asymmetric Synthesis and Catalysis

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,500

Funder: Deutsche Forschungsgemeinschaft