tert-Butylation of α,β-Unsaturated Nitriles by tert-Butylmercury Halides in the Presence of Iodide Ion

Glen A. Russell, Ping Chen, C. F. Yao, B. H. Kim

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20 Citations (Scopus)

Abstract

Iodide ion promotes the free radical addition of t-BuHgI to acrylonitrile to form t-BuCH2CH (CN)HgI. A facile reaction of the adduct 1-cyanoalkyl radical with t-BuHgI2-is indicated. Further promotion is observed in the presence of NH4I or PTSA/KI in a reaction now leading directly to t-BuCH2CH2CN. Protonation of the intermediate adduct radical followed by electron transfer from t-BuHgI2-is postulated. With fumaronitrile reaction of the adduct, radical [t-BuCH (CN)C·HCN] with t-BuHgI can be promoted by the addition of acids or bases. In the presence of NH4I or PTSA/KI, the reductive alkylation product is formed, while in the presence of DABCO, oxidative alkylation occurs to yield t-BuC (CN)=CHCN and t-BuC (CN)=C (CN)Bu-t. Protonation of [t-BuCH (CN)C·HCN] increases the ease of reduction while deprotonation yields an easily oxidized radical anion.

Original languageEnglish
Pages (from-to)5967-5972
Number of pages6
JournalJournal of the American Chemical Society
Volume117
Issue number22
DOIs
Publication statusPublished - 1995 Jun

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ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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