Enantioselective Csp3-Csp3 formation by nickel-catalyzed enantioconvergent cross-electrophile alkyl-alkyl coupling of unactivated alkyl halides
The pervasive occurrence of saturated stereogenic carbon centers in pharmaceuticals, agrochemicals, functional organic materials, and natural products has stimulated great efforts toward the construction of such saturated carbon centers. We report a reaction mode for the enantioselective constructio...
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Formato: | Online Artículo Texto |
Lenguaje: | English |
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American Association for the Advancement of Science
2023
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10328415/ https://www.ncbi.nlm.nih.gov/pubmed/37418514 http://dx.doi.org/10.1126/sciadv.adg9898 |
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author | Zhao, Wen-Tao Shu, Wei |
author_facet | Zhao, Wen-Tao Shu, Wei |
author_sort | Zhao, Wen-Tao |
collection | PubMed |
description | The pervasive occurrence of saturated stereogenic carbon centers in pharmaceuticals, agrochemicals, functional organic materials, and natural products has stimulated great efforts toward the construction of such saturated carbon centers. We report a reaction mode for the enantioselective construction of alkyl-alkyl bond to access saturated stereogenic carbon centers by asymmetric reductive cross-coupling between different alkyl electrophiles in good yields with great levels of enantioselectivity. This reaction mode uses only alkyl electrophiles for enantioselective C(sp3)-C(sp3) bond-formation, rendering reductive alkyl-alkyl cross-coupling as an alternative to traditional alkyl-alkyl cross-coupling reactions between alkyl nucleophiles and alkyl electrophiles to access saturated stereogenic carbon centers without the use of organometallic reagents. The reaction displays a broad scope for two alkyl electrophiles with good functional group tolerance. Mechanistic studies reveal that the reaction undergoes a single electron transfer that enabled the reductive coupling pathway to form the alkyl-alkyl bond. |
format | Online Article Text |
id | pubmed-10328415 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | American Association for the Advancement of Science |
record_format | MEDLINE/PubMed |
spelling | pubmed-103284152023-07-08 Enantioselective Csp3-Csp3 formation by nickel-catalyzed enantioconvergent cross-electrophile alkyl-alkyl coupling of unactivated alkyl halides Zhao, Wen-Tao Shu, Wei Sci Adv Physical and Materials Sciences The pervasive occurrence of saturated stereogenic carbon centers in pharmaceuticals, agrochemicals, functional organic materials, and natural products has stimulated great efforts toward the construction of such saturated carbon centers. We report a reaction mode for the enantioselective construction of alkyl-alkyl bond to access saturated stereogenic carbon centers by asymmetric reductive cross-coupling between different alkyl electrophiles in good yields with great levels of enantioselectivity. This reaction mode uses only alkyl electrophiles for enantioselective C(sp3)-C(sp3) bond-formation, rendering reductive alkyl-alkyl cross-coupling as an alternative to traditional alkyl-alkyl cross-coupling reactions between alkyl nucleophiles and alkyl electrophiles to access saturated stereogenic carbon centers without the use of organometallic reagents. The reaction displays a broad scope for two alkyl electrophiles with good functional group tolerance. Mechanistic studies reveal that the reaction undergoes a single electron transfer that enabled the reductive coupling pathway to form the alkyl-alkyl bond. American Association for the Advancement of Science 2023-07-07 /pmc/articles/PMC10328415/ /pubmed/37418514 http://dx.doi.org/10.1126/sciadv.adg9898 Text en Copyright © 2023 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC). https://creativecommons.org/licenses/by-nc/4.0/This is an open-access article distributed under the terms of the Creative Commons Attribution-NonCommercial license (https://creativecommons.org/licenses/by-nc/4.0/) , which permits use, distribution, and reproduction in any medium, so long as the resultant use is not for commercial advantage and provided the original work is properly cited. |
spellingShingle | Physical and Materials Sciences Zhao, Wen-Tao Shu, Wei Enantioselective Csp3-Csp3 formation by nickel-catalyzed enantioconvergent cross-electrophile alkyl-alkyl coupling of unactivated alkyl halides |
title | Enantioselective Csp3-Csp3 formation by nickel-catalyzed enantioconvergent cross-electrophile alkyl-alkyl coupling of unactivated alkyl halides |
title_full | Enantioselective Csp3-Csp3 formation by nickel-catalyzed enantioconvergent cross-electrophile alkyl-alkyl coupling of unactivated alkyl halides |
title_fullStr | Enantioselective Csp3-Csp3 formation by nickel-catalyzed enantioconvergent cross-electrophile alkyl-alkyl coupling of unactivated alkyl halides |
title_full_unstemmed | Enantioselective Csp3-Csp3 formation by nickel-catalyzed enantioconvergent cross-electrophile alkyl-alkyl coupling of unactivated alkyl halides |
title_short | Enantioselective Csp3-Csp3 formation by nickel-catalyzed enantioconvergent cross-electrophile alkyl-alkyl coupling of unactivated alkyl halides |
title_sort | enantioselective csp3-csp3 formation by nickel-catalyzed enantioconvergent cross-electrophile alkyl-alkyl coupling of unactivated alkyl halides |
topic | Physical and Materials Sciences |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10328415/ https://www.ncbi.nlm.nih.gov/pubmed/37418514 http://dx.doi.org/10.1126/sciadv.adg9898 |
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