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https://hdl.handle.net/2440/4713
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Type: | Journal article |
Title: | Comparison of gas phase and condensed phase SNi reactions. The competitive four- and five- centre cyclisations of the 3,4-epoxy-butoxide anion. A joint experimental and theoretical study |
Author: | Hevko, J. Dua, S. Taylor, M. Bowie, J. |
Citation: | Journal of the Chemical Society, Perkin Transactions 2, 1998; 7(7):1629-1634 |
Publisher: | ROYAL SOC CHEMISTRY |
Issue Date: | 1998 |
ISSN: | 1472-779X 1364-5471 |
Statement of Responsibility: | Hevko, John M.; Dua, Suresh; Taylor, Mark S.; Bowie, John H. |
Abstract: | Ab initio calculations [at the MP2-Fc/6-31+G(d) level] indicate that the 3,4-epoxybutoxide anion should undergo competitive SNi cyclisations (through four- and five-membered transition states) to yield the (M - H)- ions of oxetan-2-ylmethanol and tetrahydrofuran-3-ol respectively. The barriers to the transition states are comparable (ca. 70 kJ mol-1) for each process, and the latter product is the more stable by 82 kJ mol-1 at the level of theory indicated. Gas phase studies of the 3,4-epoxybutoxide anion excited by collisional activation are in accord with this scenario, and show, in addition, that deprotonated 2-oxetanylmethanol can convert to the starting material. Base treatment of 2-(oxiran-2-yl)ethan-1-ol (3,4-epoxybutan-1-ol) in two different solvent systems [10% aqueous sodium hydroxide and sodium hydride-tetrahydrofuran (both at reflux)] yields the same two products observed in the gas phase studies. However, deprotonated tetrahydrofuran-3-ol is the kinetic product in both solvent systems. |
DOI: | 10.1039/a801172i |
Published version: | http://dx.doi.org/10.1039/a801172i |
Appears in Collections: | Aurora harvest 6 Chemistry publications |
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