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Substrate dependent reaction channels of the Wolff–Kishner reduction reaction: A theoretical study
Wolff–Kishner reduction reactions were investigated by DFT calculations for the first time. B3LYP/6-311+G(d,p) SCRF=(PCM, solvent = 1,2-ethanediol) optimizations were carried out. To investigate the role of the base catalyst, the base-free reaction was examined by the use of acetone, hydrazine (H(2)...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Beilstein-Institut
2014
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3943666/ https://www.ncbi.nlm.nih.gov/pubmed/24605145 http://dx.doi.org/10.3762/bjoc.10.21 |
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author | Yamabe, Shinichi Zeng, Guixiang Guan, Wei Sakaki, Shigeyoshi |
author_facet | Yamabe, Shinichi Zeng, Guixiang Guan, Wei Sakaki, Shigeyoshi |
author_sort | Yamabe, Shinichi |
collection | PubMed |
description | Wolff–Kishner reduction reactions were investigated by DFT calculations for the first time. B3LYP/6-311+G(d,p) SCRF=(PCM, solvent = 1,2-ethanediol) optimizations were carried out. To investigate the role of the base catalyst, the base-free reaction was examined by the use of acetone, hydrazine (H(2)N–NH(2)) and (H(2)O)(8). A ready reaction channel of acetone → acetone hydrazine (Me(2)C=N–NH(2)) was obtained. The channel involves two likely proton-transfer routes. However, it was found that the base-free reaction was unlikely at the N(2) extrusion step from the isopropyl diimine intermediate (Me(2)C(H)–N=N–H). Two base-catalyzed reactions were investigated by models of the ketone, H(2)N–NH(2) and OH(−)(H(2)O)(7). Here, ketones are acetone and acetophenone. While routes of the ketone → hydrazone → diimine are similar, those from the diimines are different. From the isopropyl diimine, the N(2) extrusion and the C–H bond formation takes place concomitantly. The concomitance leads to the propane product concertedly. From the (1-phenyl)ethyl substituted diimine, a carbanion intermediate is formed. The para carbon of the phenyl ring of the anion is subject to the protonation, which leads to a 3-ethylidene-1,4-cyclohexadiene intermediate. Its [1,5]-hydrogen migration gives the ethylbenzene product. For both ketone substrates, the diimines undergoing E2 reactions were found to be key intermediates. |
format | Online Article Text |
id | pubmed-3943666 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2014 |
publisher | Beilstein-Institut |
record_format | MEDLINE/PubMed |
spelling | pubmed-39436662014-03-06 Substrate dependent reaction channels of the Wolff–Kishner reduction reaction: A theoretical study Yamabe, Shinichi Zeng, Guixiang Guan, Wei Sakaki, Shigeyoshi Beilstein J Org Chem Full Research Paper Wolff–Kishner reduction reactions were investigated by DFT calculations for the first time. B3LYP/6-311+G(d,p) SCRF=(PCM, solvent = 1,2-ethanediol) optimizations were carried out. To investigate the role of the base catalyst, the base-free reaction was examined by the use of acetone, hydrazine (H(2)N–NH(2)) and (H(2)O)(8). A ready reaction channel of acetone → acetone hydrazine (Me(2)C=N–NH(2)) was obtained. The channel involves two likely proton-transfer routes. However, it was found that the base-free reaction was unlikely at the N(2) extrusion step from the isopropyl diimine intermediate (Me(2)C(H)–N=N–H). Two base-catalyzed reactions were investigated by models of the ketone, H(2)N–NH(2) and OH(−)(H(2)O)(7). Here, ketones are acetone and acetophenone. While routes of the ketone → hydrazone → diimine are similar, those from the diimines are different. From the isopropyl diimine, the N(2) extrusion and the C–H bond formation takes place concomitantly. The concomitance leads to the propane product concertedly. From the (1-phenyl)ethyl substituted diimine, a carbanion intermediate is formed. The para carbon of the phenyl ring of the anion is subject to the protonation, which leads to a 3-ethylidene-1,4-cyclohexadiene intermediate. Its [1,5]-hydrogen migration gives the ethylbenzene product. For both ketone substrates, the diimines undergoing E2 reactions were found to be key intermediates. Beilstein-Institut 2014-01-23 /pmc/articles/PMC3943666/ /pubmed/24605145 http://dx.doi.org/10.3762/bjoc.10.21 Text en Copyright © 2014, Yamabe et al. https://creativecommons.org/licenses/by/2.0https://www.beilstein-journals.org/bjoc/termsThis is an Open Access article under the terms of the Creative Commons Attribution License (https://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. The license is subject to the Beilstein Journal of Organic Chemistry terms and conditions: (https://www.beilstein-journals.org/bjoc/terms) |
spellingShingle | Full Research Paper Yamabe, Shinichi Zeng, Guixiang Guan, Wei Sakaki, Shigeyoshi Substrate dependent reaction channels of the Wolff–Kishner reduction reaction: A theoretical study |
title | Substrate dependent reaction channels of the Wolff–Kishner reduction reaction: A theoretical study |
title_full | Substrate dependent reaction channels of the Wolff–Kishner reduction reaction: A theoretical study |
title_fullStr | Substrate dependent reaction channels of the Wolff–Kishner reduction reaction: A theoretical study |
title_full_unstemmed | Substrate dependent reaction channels of the Wolff–Kishner reduction reaction: A theoretical study |
title_short | Substrate dependent reaction channels of the Wolff–Kishner reduction reaction: A theoretical study |
title_sort | substrate dependent reaction channels of the wolff–kishner reduction reaction: a theoretical study |
topic | Full Research Paper |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3943666/ https://www.ncbi.nlm.nih.gov/pubmed/24605145 http://dx.doi.org/10.3762/bjoc.10.21 |
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