Mechanistic insights into the challenges of organocatalytic Beckmann rearrangement reactions

Melin Tataroğlu, Fethiye Aylin Sungur*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

Organocatalytic Beckmann rearrangement (BKR) reactions are of great interest for synthetic chemists interested in “green chemistry”. There are different proposals for the reaction mechanism depending on the experimental conditions. Clarifying the details of the BKR reaction mechanism is important for the selectivity of amides and lactams yet to be synthesized. In this study, the DFT computational method at the M06-2X/6-31+G(d,p) level of theory in conjunction with the implicit PCM solvation method has been used to elucidate alternative pathways for the Beckmann rearrangement reaction at elevated temperatures. The results enabled us to explain details of the Beckmann rearrangement reaction via a Meisenheimer complex where the process was thermodynamically driven. Meisenheimer complexes are found to be highly stable species due to the presence of aromatic ring systems allowing electron delocalization.

Original languageEnglish
Pages (from-to)1254-1263
Number of pages10
JournalOrganic and Biomolecular Chemistry
Volume21
Issue number6
DOIs
Publication statusPublished - 29 Dec 2022

Bibliographical note

Publisher Copyright:
© 2023 The Royal Society of Chemistry.

Funding

We acknowledge the support from the TÜBİTAK project (113Z218). Computational sources were provided by the National High Performance Computing Center at ITU (Grant Number: 1002282012).

FundersFunder number
International Technological University1002282012
Türkiye Bilimsel ve Teknolojik Araştırma Kurumu113Z218
Sheikh Bahaei National High Performance Computing Center, Isfahan University of Technology

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