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Substrate-Directed Enantioselective Aziridination of Alkenyl Alcohols Controlled by a Chiral Cation
[Image: see text] Alkene aziridination is a highly versatile transformation for the construction of chiral nitrogen-containing compounds. Inspired by the success of analogous substrate-directed epoxidations, we report an enantioselective aziridination of alkenyl alcohols, which enables asymmetric ni...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2023
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10080694/ https://www.ncbi.nlm.nih.gov/pubmed/36961353 http://dx.doi.org/10.1021/jacs.3c00693 |
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author | Fanourakis, Alexander Hodson, Nicholas J. Lit, Arthur R. Phipps, Robert J. |
author_facet | Fanourakis, Alexander Hodson, Nicholas J. Lit, Arthur R. Phipps, Robert J. |
author_sort | Fanourakis, Alexander |
collection | PubMed |
description | [Image: see text] Alkene aziridination is a highly versatile transformation for the construction of chiral nitrogen-containing compounds. Inspired by the success of analogous substrate-directed epoxidations, we report an enantioselective aziridination of alkenyl alcohols, which enables asymmetric nitrene transfer to alkenes with varied substitution patterns, including those not covered by the current protocols. We believe that our method is effective because it is substrate-directed, exploiting a network of attractive non-covalent interactions between the substrate, an achiral dianionic rhodium(II,II) tetracarboxylate dimer, and its two associated cinchona alkaloid-derived cations. It is these cations that provide a defined chiral pocket in which the aziridination can occur. In addition to a thorough evaluation of compatible alkene classes, we advance a practical mnemonic to predict reaction outcome and disclose a range of post-functionalization protocols that highlight the unique synthetic potential of the enantioenriched aziridine-alcohol products. |
format | Online Article Text |
id | pubmed-10080694 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-100806942023-04-08 Substrate-Directed Enantioselective Aziridination of Alkenyl Alcohols Controlled by a Chiral Cation Fanourakis, Alexander Hodson, Nicholas J. Lit, Arthur R. Phipps, Robert J. J Am Chem Soc [Image: see text] Alkene aziridination is a highly versatile transformation for the construction of chiral nitrogen-containing compounds. Inspired by the success of analogous substrate-directed epoxidations, we report an enantioselective aziridination of alkenyl alcohols, which enables asymmetric nitrene transfer to alkenes with varied substitution patterns, including those not covered by the current protocols. We believe that our method is effective because it is substrate-directed, exploiting a network of attractive non-covalent interactions between the substrate, an achiral dianionic rhodium(II,II) tetracarboxylate dimer, and its two associated cinchona alkaloid-derived cations. It is these cations that provide a defined chiral pocket in which the aziridination can occur. In addition to a thorough evaluation of compatible alkene classes, we advance a practical mnemonic to predict reaction outcome and disclose a range of post-functionalization protocols that highlight the unique synthetic potential of the enantioenriched aziridine-alcohol products. American Chemical Society 2023-03-24 /pmc/articles/PMC10080694/ /pubmed/36961353 http://dx.doi.org/10.1021/jacs.3c00693 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Fanourakis, Alexander Hodson, Nicholas J. Lit, Arthur R. Phipps, Robert J. Substrate-Directed Enantioselective Aziridination of Alkenyl Alcohols Controlled by a Chiral Cation |
title | Substrate-Directed
Enantioselective Aziridination
of Alkenyl Alcohols Controlled by a Chiral Cation |
title_full | Substrate-Directed
Enantioselective Aziridination
of Alkenyl Alcohols Controlled by a Chiral Cation |
title_fullStr | Substrate-Directed
Enantioselective Aziridination
of Alkenyl Alcohols Controlled by a Chiral Cation |
title_full_unstemmed | Substrate-Directed
Enantioselective Aziridination
of Alkenyl Alcohols Controlled by a Chiral Cation |
title_short | Substrate-Directed
Enantioselective Aziridination
of Alkenyl Alcohols Controlled by a Chiral Cation |
title_sort | substrate-directed
enantioselective aziridination
of alkenyl alcohols controlled by a chiral cation |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10080694/ https://www.ncbi.nlm.nih.gov/pubmed/36961353 http://dx.doi.org/10.1021/jacs.3c00693 |
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