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Transition metal-free catalytic reduction of primary amides using an abnormal NHC based potassium complex: integrating nucleophilicity with Lewis acidic activation
An abnormal N-heterocyclic carbene (aNHC) based potassium complex was used as a transition metal-free catalyst for reduction of primary amides to corresponding primary amines under ambient conditions. Only 2 mol% loading of the catalyst exhibits a broad substrate scope including aromatic, aliphatic...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2019
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8148392/ https://www.ncbi.nlm.nih.gov/pubmed/34123278 http://dx.doi.org/10.1039/c9sc05953a |
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author | Bhunia, Mrinal Sahoo, Sumeet Ranjan Das, Arpan Ahmed, Jasimuddin P., Sreejyothi Mandal, Swadhin K. |
author_facet | Bhunia, Mrinal Sahoo, Sumeet Ranjan Das, Arpan Ahmed, Jasimuddin P., Sreejyothi Mandal, Swadhin K. |
author_sort | Bhunia, Mrinal |
collection | PubMed |
description | An abnormal N-heterocyclic carbene (aNHC) based potassium complex was used as a transition metal-free catalyst for reduction of primary amides to corresponding primary amines under ambient conditions. Only 2 mol% loading of the catalyst exhibits a broad substrate scope including aromatic, aliphatic and heterocyclic primary amides with excellent functional group tolerance. This method was applicable for reduction of chiral amides and utilized for the synthesis of pharmaceutically valuable precursors on a gram scale. During mechanistic investigation, several intermediates were isolated and characterized through spectroscopic techniques and one of the catalytic intermediates was characterized through single-crystal XRD. A well-defined catalyst and isolable intermediate along with several stoichiometric experiments, in situ NMR experiments and the DFT study helped us to sketch the mechanistic pathway for this reduction process unravelling the dual role of the catalyst involving nucleophilic activation by aNHC along with Lewis acidic activation by K ions. |
format | Online Article Text |
id | pubmed-8148392 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-81483922021-06-11 Transition metal-free catalytic reduction of primary amides using an abnormal NHC based potassium complex: integrating nucleophilicity with Lewis acidic activation Bhunia, Mrinal Sahoo, Sumeet Ranjan Das, Arpan Ahmed, Jasimuddin P., Sreejyothi Mandal, Swadhin K. Chem Sci Chemistry An abnormal N-heterocyclic carbene (aNHC) based potassium complex was used as a transition metal-free catalyst for reduction of primary amides to corresponding primary amines under ambient conditions. Only 2 mol% loading of the catalyst exhibits a broad substrate scope including aromatic, aliphatic and heterocyclic primary amides with excellent functional group tolerance. This method was applicable for reduction of chiral amides and utilized for the synthesis of pharmaceutically valuable precursors on a gram scale. During mechanistic investigation, several intermediates were isolated and characterized through spectroscopic techniques and one of the catalytic intermediates was characterized through single-crystal XRD. A well-defined catalyst and isolable intermediate along with several stoichiometric experiments, in situ NMR experiments and the DFT study helped us to sketch the mechanistic pathway for this reduction process unravelling the dual role of the catalyst involving nucleophilic activation by aNHC along with Lewis acidic activation by K ions. The Royal Society of Chemistry 2019-12-27 /pmc/articles/PMC8148392/ /pubmed/34123278 http://dx.doi.org/10.1039/c9sc05953a Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/ |
spellingShingle | Chemistry Bhunia, Mrinal Sahoo, Sumeet Ranjan Das, Arpan Ahmed, Jasimuddin P., Sreejyothi Mandal, Swadhin K. Transition metal-free catalytic reduction of primary amides using an abnormal NHC based potassium complex: integrating nucleophilicity with Lewis acidic activation |
title | Transition metal-free catalytic reduction of primary amides using an abnormal NHC based potassium complex: integrating nucleophilicity with Lewis acidic activation |
title_full | Transition metal-free catalytic reduction of primary amides using an abnormal NHC based potassium complex: integrating nucleophilicity with Lewis acidic activation |
title_fullStr | Transition metal-free catalytic reduction of primary amides using an abnormal NHC based potassium complex: integrating nucleophilicity with Lewis acidic activation |
title_full_unstemmed | Transition metal-free catalytic reduction of primary amides using an abnormal NHC based potassium complex: integrating nucleophilicity with Lewis acidic activation |
title_short | Transition metal-free catalytic reduction of primary amides using an abnormal NHC based potassium complex: integrating nucleophilicity with Lewis acidic activation |
title_sort | transition metal-free catalytic reduction of primary amides using an abnormal nhc based potassium complex: integrating nucleophilicity with lewis acidic activation |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8148392/ https://www.ncbi.nlm.nih.gov/pubmed/34123278 http://dx.doi.org/10.1039/c9sc05953a |
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