Improved Synthetic Utility of a Sluggish Electrophile: Reaction of Chlorosulfonyl Isocyanate with Unreactive and Reactive Alkenes

Dale F. Shellhamer; Kelsey L. Alexander; Summer A. Bunting; Sarah L. Elwin; Christine J. Licata; Jacob C. Milligan; Ryan D. Robinson; Danielle E. Shipowick; Lincoln B. Smith; Marc C. Perry

doi:10.1055/s-0034-1380553

Synthesis, Table of Contents

Synthesis 2015; 47(13): 1944-1950
DOI: 10.1055/s-0034-1380553

paper

Improved Synthetic Utility of a Sluggish Electrophile: Reaction of Chlorosulfonyl Isocyanate with Unreactive and Reactive Alkenes

Dale F. Shellhamer*

Department of Chemistry, Point Loma Nazarene University, 3900 Lomaland Drive, San Diego, CA 92106-2899, USA Email: dshellha@pointloma.edu

,

Kelsey L. Alexander

Department of Chemistry, Point Loma Nazarene University, 3900 Lomaland Drive, San Diego, CA 92106-2899, USA Email: dshellha@pointloma.edu

,

Summer A. Bunting

Department of Chemistry, Point Loma Nazarene University, 3900 Lomaland Drive, San Diego, CA 92106-2899, USA Email: dshellha@pointloma.edu

,

Sarah L. Elwin

Department of Chemistry, Point Loma Nazarene University, 3900 Lomaland Drive, San Diego, CA 92106-2899, USA Email: dshellha@pointloma.edu

,

Christine J. Licata

Department of Chemistry, Point Loma Nazarene University, 3900 Lomaland Drive, San Diego, CA 92106-2899, USA Email: dshellha@pointloma.edu

,

Jacob C. Milligan

Department of Chemistry, Point Loma Nazarene University, 3900 Lomaland Drive, San Diego, CA 92106-2899, USA Email: dshellha@pointloma.edu

,

Ryan D. Robinson

Department of Chemistry, Point Loma Nazarene University, 3900 Lomaland Drive, San Diego, CA 92106-2899, USA Email: dshellha@pointloma.edu

,

Danielle E. Shipowick

Department of Chemistry, Point Loma Nazarene University, 3900 Lomaland Drive, San Diego, CA 92106-2899, USA Email: dshellha@pointloma.edu

,

Lincoln B. Smith

Department of Chemistry, Point Loma Nazarene University, 3900 Lomaland Drive, San Diego, CA 92106-2899, USA Email: dshellha@pointloma.edu

,

Marc C. Perry

Department of Chemistry, Point Loma Nazarene University, 3900 Lomaland Drive, San Diego, CA 92106-2899, USA Email: dshellha@pointloma.edu

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Abstract

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Abstract

Chlorosulfonyl isocyanate (CSI) is a sluggish electrophile in reactions with electron-deficient alkenes or with many monofluoroalkenes. The efficiency of these reactions is improved at temperatures between –15 and 25 °C because, at these temperatures, CSI and the alkene are in equilibrium with an intermediate. A unimolecular reaction of the intermediate at a temperature between –15 and 25 °C is more efficient than the bimolecular reaction of the dissociated reagents above room temperature. This finding provides a method for improving the reactions of CSI with unreactive alkenes.

Key words

electrophilic additions - alkenes - amides - radical cations - complexes - cycloadditions

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References

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