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Control of the ambident reactivity of the nitrite ion
KTH, Skolan för kemivetenskap (CHE), Kemi.
KTH, Skolan för kemivetenskap (CHE), Kemi.
KTH, Skolan för kemivetenskap (CHE), Kemi.
KTH, Skolan för kemivetenskap (CHE), Kemi.
Vise andre og tillknytning
2013 (engelsk)Inngår i: Organic and biomolecular chemistry, ISSN 1477-0520, E-ISSN 1477-0539, Vol. 11, nr 4, s. 648-653Artikkel i tidsskrift (Fagfellevurdert) 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.

sted, utgiver, år, opplag, sider
2013. Vol. 11, nr 4, s. 648-653
Emneord [en]
Alkyl Nitrites, Carbohydrate Epimerization, Substitution-Reactions, Hydrolysis, System, Nucleophiles, Activation, Inversion, Epoxides, Benzoate
HSV kategori
Identifikatorer
URN: urn:nbn:se:kth:diva-116421DOI: 10.1039/c2ob26980eISI: 000312555800017Scopus ID: 2-s2.0-84871792087OAI: oai:DiVA.org:kth-116421DiVA, id: diva2:589925
Forskningsfinansiär
Swedish Research Council
Merknad

QC 20130121

Tilgjengelig fra: 2013-01-21 Laget: 2013-01-18 Sist oppdatert: 2017-12-06bibliografisk kontrollert

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