Dual roles for potassium hydride in haloarene reduction: CSNAr and SET reduction via organic electron donors formed in benzene

Joshua P. Barham, Samuel E. Dalton, Mark Allison, Giuseppe Nocera, Allan Young, Matthew P. John, Thomas McGuire, Sébastien Campos, Tell Tuttle, John A. Murphy

Research output: Contribution to journalArticle

13 Citations (Scopus)
19 Downloads (Pure)

Abstract

Potassium hydride behaves uniquely and differently than sodium hydride towards aryl halides. Its reactions with a range of haloarenes, including designed 2,6-dialkylhaloarenes, were studied in THF and in benzene. In THF, evidence supports concerted nucleophilic aromatic substitution, CSNAr, and the mechanism originally proposed by Pierre et al. is now validated through DFT studies. In benzene, besides this pathway, strong evidence for single electron transfer chemistry is reported. Experimental observations and DFT studies lead us to propose organic super electron donor generation to initiate BHAS (base-promoted homolytic aromatic substitution) cycles. Organic donor formation originates from deprotonation of benzene by KH; attack on benzene by the resulting phenylpotassium generates phenylcyclohexadienylpotassium that can undergo (i) deprotonation to form an organic super electron donor or (ii) hydride loss to afford biphenyl. Until now, BHAS reactions have been triggered by reaction of a base, MOtBu (M = K, Na), with many different types of organic additive, all containing heteroatoms (N or O or S) that enhance their acidity and place them within range of MOtBu as a base. This paper shows that with the stronger base, KH, even a hydrocarbon (benzene) can be converted into an electron-donating initiator.
Original languageEnglish
Pages (from-to)11510-11518
Number of pages9
JournalJournal of the American Chemical Society
Volume140
Issue number36
Early online date17 Aug 2018
DOIs
Publication statusE-pub ahead of print - 17 Aug 2018

Keywords

  • potassium hydride
  • sodium hydride
  • ahaloarene reduction
  • benzene

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