Issue 6, 2018, Issue in Progress

Computational elucidation of the reaction mechanism for synthesis of pyrrolidinedione derivatives via Nef-type rearrangement – cyclization reaction

Abstract

This paper reports a quantum chemical study of all stages of a one-pot synthesis of pyrrolidinedione derivatives from nitromethane and coumarin, which includes Michael addition, migration of an oxygen atom (Nef-type rearrangement), and cyclization to a pyrrolidine ring. The energy barrier of deprotonated nitromethane addition to coumarin is 21.7 kJ mol−1, while the barrier of proton transfer from the methylene to the nitro group in the nitromethyl group is notably higher, 197.8 kJ mol−1. The second stage of the reaction, migration of an oxygen atom within the nitromethyl group, occurs with lowest energy barrier, 142.4 kJ mol−1, when it is assisted by an additional water molecule. The last stage – cyclization, passes with a very low energy barrier of 11.9 kJ mol−1 but the tautomerization of the nitrosohydroxymethyl group to the hydroxy-N-hydroxyiminomethyl, necessary for the process, has an energy barrier of 178.4 kJ mol−1. Analogous calculations for the same process with the ethyl ester of 3-coumarin-carboxylic acid as substrate show that the relative energies of the intermediates and transition states are by at most 10–16 kJ mol−1 more stable than the corresponding structures with coumarin.

Graphical abstract: Computational elucidation of the reaction mechanism for synthesis of pyrrolidinedione derivatives via Nef-type rearrangement – cyclization reaction

Supplementary files

Article information

Article type
Paper
Submitted
29 Oct 2017
Accepted
08 Jan 2018
First published
16 Jan 2018
This article is Open Access
Creative Commons BY license

RSC Adv., 2018,8, 3178-3188

Computational elucidation of the reaction mechanism for synthesis of pyrrolidinedione derivatives via Nef-type rearrangement – cyclization reaction

E. D. Ilieva, G. P. Petrova, R. D. Nikolova and G. N. Vayssilov, RSC Adv., 2018, 8, 3178 DOI: 10.1039/C7RA11908A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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