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Stereochemistry of beta-deuterium isotope effects on amine basicity.
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2005 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 127, no 26, p. 9641-7Article in journal (Refereed) Published
Abstract [en]

Secondary beta-deuterium isotope effects on amine basicities are measured using a remarkably precise NMR titration method. Deuteration is found to increase the basicity of methylamine, dimethylamine, benzylamine, N,N-dimethylaniline, 2-methyl-2-azanorbornane, and pyrrolizidine. The increase in dimethylamine arises entirely from enthalpy, contrary to a previous report. The method permits a determination of intramolecular isotope effects in 1-benzyl-4-methylpiperidine and 2-benzyl-2-azanorbornane. It is found that deuteration has a larger isotope effect when either antiperiplanar or synperiplanar to a lone pair, but the synperiplanar effect is smaller, as confirmed by computations. The isotope effect is attributed to a lowered zero-point energy of a C-H bond adjacent to an amine nitrogen, arising from delocalization of either a syn or an anti lone pair, and with no detectable angle-independent inductive effect.

Place, publisher, year, edition, pages
2005. Vol. 127, no 26, p. 9641-7
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Organic Chemistry
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URN: urn:nbn:se:uu:diva-369306DOI: 10.1021/ja0511927PubMedID: 15984892OAI: oai:DiVA.org:uu-369306DiVA, id: diva2:1275770
Available from: 2019-01-07 Created: 2019-01-07 Last updated: 2019-01-07

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Erdélyi, Máté

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