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Copper-catalyzed asymmetric C(sp(3))-H cyanoalkylation of glycine derivatives and peptides
Alkylnitriles play important roles in many fields because of their unique electronic properties and structural characteristics. Incorporating cyanoalkyl with characteristic spectroscopy and reactivity properties into amino acids and peptides is of special interest for potential imaging and therapeut...
Autores principales: | , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2023
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10244411/ https://www.ncbi.nlm.nih.gov/pubmed/37280209 http://dx.doi.org/10.1038/s41467-023-38871-1 |
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author | Qi, Rupeng Chen, Qiao Liu, Liangyu Ma, Zijian Pan, Da Wang, Hongying Li, Zhixuan Wang, Chao Xu, Zhaoqing |
author_facet | Qi, Rupeng Chen, Qiao Liu, Liangyu Ma, Zijian Pan, Da Wang, Hongying Li, Zhixuan Wang, Chao Xu, Zhaoqing |
author_sort | Qi, Rupeng |
collection | PubMed |
description | Alkylnitriles play important roles in many fields because of their unique electronic properties and structural characteristics. Incorporating cyanoalkyl with characteristic spectroscopy and reactivity properties into amino acids and peptides is of special interest for potential imaging and therapeutic purposes. Here, we report a copper-catalyzed asymmetric cyanoalkylation of C(sp(3))-H. In the reactions, glycine derivatives can effectively couple with various cycloalkanone oxime esters with high enantioselectivities, and the reaction can be applied to the late-stage modification of peptides with good yields and excellent stereoselectivities, which is useful for modern peptide synthesis and drug discovery. The mechanistic studies show that the in situ formed copper complex by the coordination of glycine derivatives and chiral phosphine Cu catalyst can not only mediate the single electronic reduction of cycloalkanone oxime ester but also control the stereoselectivity of the cyanoalkylation reaction. |
format | Online Article Text |
id | pubmed-10244411 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-102444112023-06-08 Copper-catalyzed asymmetric C(sp(3))-H cyanoalkylation of glycine derivatives and peptides Qi, Rupeng Chen, Qiao Liu, Liangyu Ma, Zijian Pan, Da Wang, Hongying Li, Zhixuan Wang, Chao Xu, Zhaoqing Nat Commun Article Alkylnitriles play important roles in many fields because of their unique electronic properties and structural characteristics. Incorporating cyanoalkyl with characteristic spectroscopy and reactivity properties into amino acids and peptides is of special interest for potential imaging and therapeutic purposes. Here, we report a copper-catalyzed asymmetric cyanoalkylation of C(sp(3))-H. In the reactions, glycine derivatives can effectively couple with various cycloalkanone oxime esters with high enantioselectivities, and the reaction can be applied to the late-stage modification of peptides with good yields and excellent stereoselectivities, which is useful for modern peptide synthesis and drug discovery. The mechanistic studies show that the in situ formed copper complex by the coordination of glycine derivatives and chiral phosphine Cu catalyst can not only mediate the single electronic reduction of cycloalkanone oxime ester but also control the stereoselectivity of the cyanoalkylation reaction. Nature Publishing Group UK 2023-06-06 /pmc/articles/PMC10244411/ /pubmed/37280209 http://dx.doi.org/10.1038/s41467-023-38871-1 Text en © The Author(s) 2023 https://creativecommons.org/licenses/by/4.0/Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) . |
spellingShingle | Article Qi, Rupeng Chen, Qiao Liu, Liangyu Ma, Zijian Pan, Da Wang, Hongying Li, Zhixuan Wang, Chao Xu, Zhaoqing Copper-catalyzed asymmetric C(sp(3))-H cyanoalkylation of glycine derivatives and peptides |
title | Copper-catalyzed asymmetric C(sp(3))-H cyanoalkylation of glycine derivatives and peptides |
title_full | Copper-catalyzed asymmetric C(sp(3))-H cyanoalkylation of glycine derivatives and peptides |
title_fullStr | Copper-catalyzed asymmetric C(sp(3))-H cyanoalkylation of glycine derivatives and peptides |
title_full_unstemmed | Copper-catalyzed asymmetric C(sp(3))-H cyanoalkylation of glycine derivatives and peptides |
title_short | Copper-catalyzed asymmetric C(sp(3))-H cyanoalkylation of glycine derivatives and peptides |
title_sort | copper-catalyzed asymmetric c(sp(3))-h cyanoalkylation of glycine derivatives and peptides |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10244411/ https://www.ncbi.nlm.nih.gov/pubmed/37280209 http://dx.doi.org/10.1038/s41467-023-38871-1 |
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