Foley, David A. and Doecke, Christopher W. and Buser, Jonas Y. and Merritt, Jeremy M. and Murphy, Linda and Kissane, Marie and Collins, Stuart G. and Maguire, Anita R. and Kaerner, Andreas

2011

Journal of Organic Chemistry

ReactNMR and ReactIR as Reaction Monitoring and Mechanistic Elucidation Tools: The NCS Mediated Cascade Reaction of alpha-Thioamides to alpha-Thio-beta-chloroacrylamides

Validated

()

76

23

9630

9640

On-flow ReactIR and (1)H NMR reaction monitoring, coupled with in situ intermediate characterization, was used to aid in the mechanistic elucidation of the N-chlorosuccinirnide mediated transformation of an alpha-athioarnide. Multiple intermediates in this reaction cascade are identified and characterized, and in particular, spectroscopic evidence for the intermediacy of the chlorosulfonium ion in the chlorination of alpha-thioamides is provided. Further to this, solvent effects on the outcome of the transformation are discussed. This work also demonstrates the utility of using a combination of ReactIR and flow NMR reaction monitoring (ReactNMR) for characterizing complex multicomponent reaction mixtures.