1,4,7-Trimethyloxatriquinane: SN2 Reaction at Tertiary Carbon
- 16 July 2010
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 132 (31), 10662-10664
- https://doi.org/10.1021/ja103880c
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 S(N)1 pathway is excluded, the only reasonable mechanistic interpretation for the reaction between 1 and N(3)(-) is S(N)2, 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.Keywords
This publication has 12 references indexed in Scilit:
- Can One Predict Changes from SN1 to SN2 Mechanisms?Journal of the American Chemical Society, 2009
- Taming the Highly Reactive Oxonium IonAngewandte Chemie-International Edition, 2009
- Oxatriquinane and Oxatriquinacene: Extraordinary Oxonium IonsJournal of the American Chemical Society, 2008
- SN2 Displacement at Tertiary CarbonCanadian Journal of Chemistry, 1974
- Nucleophilic displacement at tertiary carbonTetrahedron Letters, 1973
- Ion-pair SN2 reactions at a tertiary centerJournal of the American Chemical Society, 1972
- Halide exchange at a saturated carbon atom in dimethylformamide solvent. Comparison of experimental rates and Arrhenius parameters with values calculated by IngoldJournal of the Chemical Society B: Physical Organic, 1968
- Direct Nucleophilic Substitution at the Central Carbon Atom of Triarylmethyl Substrates1Journal of the American Chemical Society, 1966
- Alleged SN2 finkelstein substitutions of t-butyl bromideTetrahedron Letters, 1959
- Mechanism of substitution at a saturated carbon atom. Part XLIII. Kinetics of the interaction of chloride ions with simple alkyl bromides in acetoneJournal of the Chemical Society, 1955