Amine Induced Retardation of the Radical-Mediated Thiol–Ene Reaction via the Formation of Metastable Disulfide Radical Anions

  • Dillon M. Love (4841175)
  • Kangmin Kim (1578019)
  • John T. Goodrich (4841178)
  • Benjamin D. Fairbanks (1265784)
  • Brady T. Worrell (1861012)
  • Mark P. Stoykovich (1318590)
  • Charles B. Musgrave (1275567)
  • Christopher N. Bowman (1265787)
Publication date
February 2018

Abstract

The effect of amines on the kinetics and efficacy of radical-mediated thiol–ene coupling (TEC) reactions was investigated. By varying the thiol reactant and amine additive, it was shown that amines retard thiyl radical-mediated reactions when the amine is adequately basic enough to deprotonate the thiol affording the thiolate anion, e.g., when the weakly basic amine tetramethylethylenediamine was incorporated in the TEC reaction between butyl 2-mercaptoacetate and an allyl ether at 5 mol %, the final conversion was reduced from quantitative to <40%. Alternatively, no effect is observed when the less acidic thiol butyl 3-mercaptopropionate is employed. The thiolate anion was established as the retarding species through the introduction of am...

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