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 language | English |
|---|---|
| Pages (from-to) | 1254-1263 |
| Number of pages | 10 |
| Journal | Organic and Biomolecular Chemistry |
| Volume | 21 |
| Issue number | 6 |
| DOIs | |
| Publication status | Published - 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).
| Funders | Funder number |
|---|---|
| International Technological University | 1002282012 |
| Türkiye Bilimsel ve Teknolojik Araştırma Kurumu | 113Z218 |
| Sheikh Bahaei National High Performance Computing Center, Isfahan University of Technology |