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Issue 4, 2013
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Control of the ambident reactivity of the nitrite ion

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Abstract

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.

Graphical abstract: Control of the ambident reactivity of the nitrite ion

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Article information


Submitted
07 Jun 2012
Accepted
07 Nov 2012
First published
08 Nov 2012

Org. Biomol. Chem., 2013,11, 648-653
Article type
Paper

Control of the ambident reactivity of the nitrite ion

H. Dong, M. Rahm, N. Thota, L. Deng, T. Brinck and O. Ramström, Org. Biomol. Chem., 2013, 11, 648
DOI: 10.1039/C2OB26980E

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