Foley, DA,Doecke, CW,Buser, JY,Merritt, JM,Murphy, L,Kissane, M,Collins, SG,Maguire, AR,Kaerner, A

2011

January

The 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

()

RESOLUTION NMR-SPECTROSCOPY FLOW NMR ONLINE NMR CHEMICAL-REACTIONS IN-SITU INTERMEDIATE 2,4,6-TRINITROANISOLE TRANSFORMATION KINETICS STEP

76

9630

9640

On-flow ReactIR and H-1 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.

DOI 10.1021/jo201212p