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 language | English |
|---|---|
| Pages (from-to) | 5967-5972 |
| Number of pages | 6 |
| Journal | Journal of the American Chemical Society |
| Volume | 117 |
| Issue number | 22 |
| DOIs | |
| Publication status | Published - 1995 Jun |
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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 journal › Article
}
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.
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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 -