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Prediction of NHC-catalyzed chemoselective functionalizations of carbonyl compounds: a general mechanistic map
Generally, N-heterocyclic carbene (NHC) complexed with carbonyl compounds would transform into several important active intermediates, i.e., enolates, Breslow intermediates, or acylazolium intermediates, which act as either a nucleophile (Nu) or an electrophile (E) to react with the other E/Nu partn...
Autores principales: | , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8159411/ https://www.ncbi.nlm.nih.gov/pubmed/34123007 http://dx.doi.org/10.1039/d0sc01793k |
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author | Li, Xue Xu, Jun Li, Shi-Jun Qu, Ling-Bo Li, Zhongjun Chi, Yonggui Robin Wei, Donghui Lan, Yu |
author_facet | Li, Xue Xu, Jun Li, Shi-Jun Qu, Ling-Bo Li, Zhongjun Chi, Yonggui Robin Wei, Donghui Lan, Yu |
author_sort | Li, Xue |
collection | PubMed |
description | Generally, N-heterocyclic carbene (NHC) complexed with carbonyl compounds would transform into several important active intermediates, i.e., enolates, Breslow intermediates, or acylazolium intermediates, which act as either a nucleophile (Nu) or an electrophile (E) to react with the other E/Nu partner. Hence, the key to predicting the origin of chemoselectivity is to compute the activity (i.e., electrophilic index ω for E and nucleophilic index N for Nu) and stability of the intermediates and products, which are suggested in a general mechanistic map of these reactions. To support this point, we selected and studied different cases of the NHC-catalyzed reactions of carbonyl compounds in the presence of a base and/or an oxidant, in which multiple possible pathways involving acylazolium, enolate, Breslow, and α,β-unsaturated acylazolium intermediates were proposed and a novel index ω + N of the E and Nu partners was employed to exactly predict the energy barrier of the chemoselective step in theory. This work provides a guide for determining the general principle behind organocatalytic reactions with various chemoselectivities, and suggests a general application of the reaction index in predicting the chemoselectivity of the nucleophilic and electrophilic reactions. |
format | Online Article Text |
id | pubmed-8159411 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-81594112021-06-11 Prediction of NHC-catalyzed chemoselective functionalizations of carbonyl compounds: a general mechanistic map Li, Xue Xu, Jun Li, Shi-Jun Qu, Ling-Bo Li, Zhongjun Chi, Yonggui Robin Wei, Donghui Lan, Yu Chem Sci Chemistry Generally, N-heterocyclic carbene (NHC) complexed with carbonyl compounds would transform into several important active intermediates, i.e., enolates, Breslow intermediates, or acylazolium intermediates, which act as either a nucleophile (Nu) or an electrophile (E) to react with the other E/Nu partner. Hence, the key to predicting the origin of chemoselectivity is to compute the activity (i.e., electrophilic index ω for E and nucleophilic index N for Nu) and stability of the intermediates and products, which are suggested in a general mechanistic map of these reactions. To support this point, we selected and studied different cases of the NHC-catalyzed reactions of carbonyl compounds in the presence of a base and/or an oxidant, in which multiple possible pathways involving acylazolium, enolate, Breslow, and α,β-unsaturated acylazolium intermediates were proposed and a novel index ω + N of the E and Nu partners was employed to exactly predict the energy barrier of the chemoselective step in theory. This work provides a guide for determining the general principle behind organocatalytic reactions with various chemoselectivities, and suggests a general application of the reaction index in predicting the chemoselectivity of the nucleophilic and electrophilic reactions. The Royal Society of Chemistry 2020-06-22 /pmc/articles/PMC8159411/ /pubmed/34123007 http://dx.doi.org/10.1039/d0sc01793k Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/ |
spellingShingle | Chemistry Li, Xue Xu, Jun Li, Shi-Jun Qu, Ling-Bo Li, Zhongjun Chi, Yonggui Robin Wei, Donghui Lan, Yu Prediction of NHC-catalyzed chemoselective functionalizations of carbonyl compounds: a general mechanistic map |
title | Prediction of NHC-catalyzed chemoselective functionalizations of carbonyl compounds: a general mechanistic map |
title_full | Prediction of NHC-catalyzed chemoselective functionalizations of carbonyl compounds: a general mechanistic map |
title_fullStr | Prediction of NHC-catalyzed chemoselective functionalizations of carbonyl compounds: a general mechanistic map |
title_full_unstemmed | Prediction of NHC-catalyzed chemoselective functionalizations of carbonyl compounds: a general mechanistic map |
title_short | Prediction of NHC-catalyzed chemoselective functionalizations of carbonyl compounds: a general mechanistic map |
title_sort | prediction of nhc-catalyzed chemoselective functionalizations of carbonyl compounds: a general mechanistic map |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8159411/ https://www.ncbi.nlm.nih.gov/pubmed/34123007 http://dx.doi.org/10.1039/d0sc01793k |
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