Abstract
The synthesis of 1,4,7-trimethyloxatriquinane (1), a 3-fold tertiary alkyl oxonium salt, is described. Compound 1 is inert to solvolysis with alcohols, even at elevated temperatures, but undergoes facile substitution with the strongly nucleophilic azide anion. Since an SN1 pathway is excluded, the only reasonable mechanistic interpretation for the reaction between 1 and N3 - is SN2, despite the fact that substitution is occurring at a tertiary carbon center. This finding is supported by computational modeling and a study of the reaction kinetics, and is also consistent with observed solvent and salt effects.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 10662-10664 |
| Number of pages | 3 |
| Journal | Journal of the American Chemical Society |
| Volume | 132 |
| Issue number | 31 |
| DOIs | |
| State | Published - Aug 11 2010 |
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ASJC Scopus subject areas
- Chemistry(all)
- Catalysis
- Biochemistry
- Colloid and Surface Chemistry
Cite this
1,4,7-trimethyloxatriquinane : SN2 reaction at tertiary carbon. / Mascal, Mark; Hafezi, Nema; Toney, Michael D.
In: Journal of the American Chemical Society, Vol. 132, No. 31, 11.08.2010, p. 10662-10664.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - 1,4,7-trimethyloxatriquinane
T2 - SN2 reaction at tertiary carbon
AU - Mascal, Mark
AU - Hafezi, Nema
AU - Toney, Michael D.
PY - 2010/8/11
Y1 - 2010/8/11
N2 - The synthesis of 1,4,7-trimethyloxatriquinane (1), a 3-fold tertiary alkyl oxonium salt, is described. Compound 1 is inert to solvolysis with alcohols, even at elevated temperatures, but undergoes facile substitution with the strongly nucleophilic azide anion. Since an SN1 pathway is excluded, the only reasonable mechanistic interpretation for the reaction between 1 and N3 - is SN2, despite the fact that substitution is occurring at a tertiary carbon center. This finding is supported by computational modeling and a study of the reaction kinetics, and is also consistent with observed solvent and salt effects.
AB - The synthesis of 1,4,7-trimethyloxatriquinane (1), a 3-fold tertiary alkyl oxonium salt, is described. Compound 1 is inert to solvolysis with alcohols, even at elevated temperatures, but undergoes facile substitution with the strongly nucleophilic azide anion. Since an SN1 pathway is excluded, the only reasonable mechanistic interpretation for the reaction between 1 and N3 - is SN2, despite the fact that substitution is occurring at a tertiary carbon center. This finding is supported by computational modeling and a study of the reaction kinetics, and is also consistent with observed solvent and salt effects.
UR - http://www.scopus.com/inward/record.url?scp=77955373368&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=77955373368&partnerID=8YFLogxK
U2 - 10.1021/ja103880c
DO - 10.1021/ja103880c
M3 - Article
C2 - 20681692
AN - SCOPUS:77955373368
VL - 132
SP - 10662
EP - 10664
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 31
ER -