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Control of the ambident reactivity of the nitrite ion
KTH, School of Chemical Science and Engineering (CHE), Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry.
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2013 (English)In: Organic and biomolecular chemistry, ISSN 1477-0520, E-ISSN 1477-0539, Vol. 11, no 4, 648-653 p.Article in journal (Refereed) Published
Abstract [en]

In previous studies, it was reported that a neighbouring equatorial ester group is essential for a good yield of nitrite-mediated triflate inversion, whereas with neighbouring benzyl ether groups or axial ester groups, mixtures are generally produced. In the present study, the origin of this difference was addressed. The ambident reactivity of the nitrite ion has been found to be the cause of the complex product formation observed, which can be controlled by a neighbouring equatorial ester group. Both N-attack and O-attack occur in the absence of the ester group, whereas O-attack is favoured in its presence. A neighbouring group assistance mechanism is proposed, in addition to steric effects, based on secondary interactions between the neighbouring ester group and the incoming nucleophile. High-level quantum mechanical calculations were carried out in order to delineate this effect. The theoretical results are in excellent agreement with experiments, and suggest a catalytic role for the neighbouring equatorial ester group.

Place, publisher, year, edition, pages
2013. Vol. 11, no 4, 648-653 p.
Keyword [en]
Alkyl Nitrites, Carbohydrate Epimerization, Substitution-Reactions, Hydrolysis, System, Nucleophiles, Activation, Inversion, Epoxides, Benzoate
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-116421DOI: 10.1039/c2ob26980eISI: 000312555800017Scopus ID: 2-s2.0-84871792087OAI: oai:DiVA.org:kth-116421DiVA: diva2:589925
Funder
Swedish Research Council
Note

QC 20130121

Available from: 2013-01-21 Created: 2013-01-18 Last updated: 2017-12-06Bibliographically approved

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Brinck, Tore

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