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

Research output: Contribution to journalArticle

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

Fingerprint

Nitriles
Protonation
Alkylation
Iodides
Ions
Acrylonitrile
Deprotonation
Free radicals
Free Radicals
Anions
Negative ions
Electrons
Acids
1,3,6,8-pyrene tetrasulfonate
fumaronitrile
triethylenediamine

ASJC Scopus subject areas

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

Cite this

tert-Butylation of α,β-Unsaturated Nitriles by tert-Butylmercury Halides in the Presence of Iodide Ion. / Russell, Glen A.; Chen, Ping; Yao, C. F.; Kim, B. H.

In: Journal of the American Chemical Society, Vol. 117, No. 22, 06.1995, p. 5967-5972.

Research output: Contribution to journalArticle

@article{ad7f645624d14e7aa7f5d8ef5609dfa5,
title = "tert-Butylation of α,β-Unsaturated Nitriles by tert-Butylmercury Halides in the Presence of Iodide Ion",
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.",
author = "Russell, {Glen A.} and Ping Chen and Yao, {C. F.} and Kim, {B. H.}",
year = "1995",
month = "6",
doi = "10.1021/ja00127a009",
language = "English",
volume = "117",
pages = "5967--5972",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "22",

}

TY - JOUR

T1 - tert-Butylation of α,β-Unsaturated Nitriles by tert-Butylmercury Halides in the Presence of Iodide Ion

AU - Russell, Glen A.

AU - Chen, Ping

AU - Yao, C. F.

AU - Kim, B. H.

PY - 1995/6

Y1 - 1995/6

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=0001764128&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0001764128&partnerID=8YFLogxK

U2 - 10.1021/ja00127a009

DO - 10.1021/ja00127a009

M3 - Article

AN - SCOPUS:0001764128

VL - 117

SP - 5967

EP - 5972

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 22

ER -