Abstract
The selective electrochemical oxidation of heteroatom compounds having two different electroauxiliaries, i.e. silicon and tin, on the same α-carbon was examined. The oxidation potentials of such compounds were found to be similar to those of the corresponding compounds having only tin, indicating the predominant role of tin over that of silicon. The HOMO levels obtained by the molecular orbital calculations were consistent with the experimental results. The molecular orbital calculation of the cation radical suggests the selective cleavage of the C-Sn bond by the oxidation. Preparative electrochemical oxidation gave rise to selective cleavage of the C-Sn bond and the introduction of a nucleophile to the carbon. The C-Si bond was not affected at all. The product can also be further oxidized using the silyl group as an electroauxiliary. The second oxidation proceeded smoothly to cleave the C-Si bond and a second nucleophile was introduced on the same carbon. The present study indicates the feasibility of the redox potential based selective sequential transformation using electroauxiliaries.
| Original language | English |
|---|---|
| Pages (from-to) | 55-65 |
| Number of pages | 11 |
| Journal | Journal of Electroanalytical Chemistry |
| Volume | 507 |
| Issue number | 1-2 |
| DOIs | |
| Publication status | Published - Jul 13 2001 |
| Externally published | Yes |
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Keywords
- Anodic oxidation
- Electroauxiliary
- Electrosynthesis
- Rotating disk electrode
ASJC Scopus subject areas
- Chemical Engineering(all)
- Analytical Chemistry
- Electrochemistry
Cite this
Selective electrochemical oxidation of heteroatom compounds having both silicon and tin on the same carbon as electroauxiliaries. / Yoshida, J. I.; Watanabe, M.; Toshioka, H.; Imagawa, M.; Suga, Seiji.
In: Journal of Electroanalytical Chemistry, Vol. 507, No. 1-2, 13.07.2001, p. 55-65.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Selective electrochemical oxidation of heteroatom compounds having both silicon and tin on the same carbon as electroauxiliaries
AU - Yoshida, J. I.
AU - Watanabe, M.
AU - Toshioka, H.
AU - Imagawa, M.
AU - Suga, Seiji
PY - 2001/7/13
Y1 - 2001/7/13
N2 - The selective electrochemical oxidation of heteroatom compounds having two different electroauxiliaries, i.e. silicon and tin, on the same α-carbon was examined. The oxidation potentials of such compounds were found to be similar to those of the corresponding compounds having only tin, indicating the predominant role of tin over that of silicon. The HOMO levels obtained by the molecular orbital calculations were consistent with the experimental results. The molecular orbital calculation of the cation radical suggests the selective cleavage of the C-Sn bond by the oxidation. Preparative electrochemical oxidation gave rise to selective cleavage of the C-Sn bond and the introduction of a nucleophile to the carbon. The C-Si bond was not affected at all. The product can also be further oxidized using the silyl group as an electroauxiliary. The second oxidation proceeded smoothly to cleave the C-Si bond and a second nucleophile was introduced on the same carbon. The present study indicates the feasibility of the redox potential based selective sequential transformation using electroauxiliaries.
AB - The selective electrochemical oxidation of heteroatom compounds having two different electroauxiliaries, i.e. silicon and tin, on the same α-carbon was examined. The oxidation potentials of such compounds were found to be similar to those of the corresponding compounds having only tin, indicating the predominant role of tin over that of silicon. The HOMO levels obtained by the molecular orbital calculations were consistent with the experimental results. The molecular orbital calculation of the cation radical suggests the selective cleavage of the C-Sn bond by the oxidation. Preparative electrochemical oxidation gave rise to selective cleavage of the C-Sn bond and the introduction of a nucleophile to the carbon. The C-Si bond was not affected at all. The product can also be further oxidized using the silyl group as an electroauxiliary. The second oxidation proceeded smoothly to cleave the C-Si bond and a second nucleophile was introduced on the same carbon. The present study indicates the feasibility of the redox potential based selective sequential transformation using electroauxiliaries.
KW - Anodic oxidation
KW - Electroauxiliary
KW - Electrosynthesis
KW - Rotating disk electrode
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UR - http://www.scopus.com/inward/citedby.url?scp=0035854239&partnerID=8YFLogxK
U2 - 10.1016/S0022-0728(01)00402-8
DO - 10.1016/S0022-0728(01)00402-8
M3 - Article
VL - 507
SP - 55
EP - 65
JO - Journal of Electroanalytical Chemistry
JF - Journal of Electroanalytical Chemistry
SN - 0368-1874
IS - 1-2
ER -