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Ritter-enabled catalytic asymmetric chloroamidation of olefins
Intermolecular asymmetric haloamination reactions are challenging due to the inherently high halenium affinity (HalA) of the nitrogen atom, which often leads to N-halogenated products as a kinetic trap. To circumvent this issue, acetonitrile, possessing a low HalA, was used as the nucleophile in the...
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/PMC8179065/ https://www.ncbi.nlm.nih.gov/pubmed/34163947 http://dx.doi.org/10.1039/d0sc05224h |
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author | Steigerwald, Daniel C. Soltanzadeh, Bardia Sarkar, Aritra Morgenstern, Cecilia C. Staples, Richard J. Borhan, Babak |
author_facet | Steigerwald, Daniel C. Soltanzadeh, Bardia Sarkar, Aritra Morgenstern, Cecilia C. Staples, Richard J. Borhan, Babak |
author_sort | Steigerwald, Daniel C. |
collection | PubMed |
description | Intermolecular asymmetric haloamination reactions are challenging due to the inherently high halenium affinity (HalA) of the nitrogen atom, which often leads to N-halogenated products as a kinetic trap. To circumvent this issue, acetonitrile, possessing a low HalA, was used as the nucleophile in the catalytic asymmetric Ritter-type chloroamidation of allyl-amides. This method is compatible with Z and E alkenes with both alkyl and aromatic substitution. Mild acidic workup reveals the 1,2-chloroamide products with enantiomeric excess greater than 95% for many examples. We also report the successful use of the sulfonamide chlorenium reagent dichloramine-T in this chlorenium-initiated catalytic asymmetric Ritter-type reaction. Facile modifications lead to chiral imidazoline, guanidine, and orthogonally protected 1,2,3 chiral tri-amines. |
format | Online Article Text |
id | pubmed-8179065 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-81790652021-06-22 Ritter-enabled catalytic asymmetric chloroamidation of olefins Steigerwald, Daniel C. Soltanzadeh, Bardia Sarkar, Aritra Morgenstern, Cecilia C. Staples, Richard J. Borhan, Babak Chem Sci Chemistry Intermolecular asymmetric haloamination reactions are challenging due to the inherently high halenium affinity (HalA) of the nitrogen atom, which often leads to N-halogenated products as a kinetic trap. To circumvent this issue, acetonitrile, possessing a low HalA, was used as the nucleophile in the catalytic asymmetric Ritter-type chloroamidation of allyl-amides. This method is compatible with Z and E alkenes with both alkyl and aromatic substitution. Mild acidic workup reveals the 1,2-chloroamide products with enantiomeric excess greater than 95% for many examples. We also report the successful use of the sulfonamide chlorenium reagent dichloramine-T in this chlorenium-initiated catalytic asymmetric Ritter-type reaction. Facile modifications lead to chiral imidazoline, guanidine, and orthogonally protected 1,2,3 chiral tri-amines. The Royal Society of Chemistry 2020-12-07 /pmc/articles/PMC8179065/ /pubmed/34163947 http://dx.doi.org/10.1039/d0sc05224h Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/ |
spellingShingle | Chemistry Steigerwald, Daniel C. Soltanzadeh, Bardia Sarkar, Aritra Morgenstern, Cecilia C. Staples, Richard J. Borhan, Babak Ritter-enabled catalytic asymmetric chloroamidation of olefins |
title | Ritter-enabled catalytic asymmetric chloroamidation of olefins |
title_full | Ritter-enabled catalytic asymmetric chloroamidation of olefins |
title_fullStr | Ritter-enabled catalytic asymmetric chloroamidation of olefins |
title_full_unstemmed | Ritter-enabled catalytic asymmetric chloroamidation of olefins |
title_short | Ritter-enabled catalytic asymmetric chloroamidation of olefins |
title_sort | ritter-enabled catalytic asymmetric chloroamidation of olefins |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8179065/ https://www.ncbi.nlm.nih.gov/pubmed/34163947 http://dx.doi.org/10.1039/d0sc05224h |
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