Cargando…

Visible-light promoted regioselective amination and alkylation of remote C(sp(3))-H bonds

The C-N cross coupling reaction has always been a fundamental task in organic synthesis. However, the direct use of N-H group of aryl amines to generate N-centered radicals which would couple with alkyl radicals to construct C-N bonds is still rare. Here we report a visible light-promoted C-N radica...

Descripción completa

Detalles Bibliográficos
Autores principales: Guo, Quanping, Peng, Qiang, Chai, Hongli, Huo, Yumei, Wang, Shan, Xu, Zhaoqing
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7081228/
https://www.ncbi.nlm.nih.gov/pubmed/32193371
http://dx.doi.org/10.1038/s41467-020-15167-2
_version_ 1783508134000590848
author Guo, Quanping
Peng, Qiang
Chai, Hongli
Huo, Yumei
Wang, Shan
Xu, Zhaoqing
author_facet Guo, Quanping
Peng, Qiang
Chai, Hongli
Huo, Yumei
Wang, Shan
Xu, Zhaoqing
author_sort Guo, Quanping
collection PubMed
description The C-N cross coupling reaction has always been a fundamental task in organic synthesis. However, the direct use of N-H group of aryl amines to generate N-centered radicals which would couple with alkyl radicals to construct C-N bonds is still rare. Here we report a visible light-promoted C-N radical cross coupling for regioselective amination of remote C(sp(3))-H bonds. Under visible light irradiation, the N-H groups of aryl amines are converted to N-centered radicals, and are then trapped by alkyl radicals, which are generated from Hofmann-Löffler-Freytag (HLF) type 1,5-hydrogen atom transfer (1,5-HAT). With the same strategy, the regioselective C(sp(3))-C(sp(3)) cross coupling is also realized by using alkyl Hantzsch esters (or nitrile) as radical alkylation reagents. Notably, the α-C(sp(3))-H of tertiary amines can be directly alkylated to form the C(sp(3))-C(sp(3)) bonds via C(sp(3))-H − C(sp(3))-H cross coupling through the same photoredox pathway.
format Online
Article
Text
id pubmed-7081228
institution National Center for Biotechnology Information
language English
publishDate 2020
publisher Nature Publishing Group UK
record_format MEDLINE/PubMed
spelling pubmed-70812282020-03-23 Visible-light promoted regioselective amination and alkylation of remote C(sp(3))-H bonds Guo, Quanping Peng, Qiang Chai, Hongli Huo, Yumei Wang, Shan Xu, Zhaoqing Nat Commun Article The C-N cross coupling reaction has always been a fundamental task in organic synthesis. However, the direct use of N-H group of aryl amines to generate N-centered radicals which would couple with alkyl radicals to construct C-N bonds is still rare. Here we report a visible light-promoted C-N radical cross coupling for regioselective amination of remote C(sp(3))-H bonds. Under visible light irradiation, the N-H groups of aryl amines are converted to N-centered radicals, and are then trapped by alkyl radicals, which are generated from Hofmann-Löffler-Freytag (HLF) type 1,5-hydrogen atom transfer (1,5-HAT). With the same strategy, the regioselective C(sp(3))-C(sp(3)) cross coupling is also realized by using alkyl Hantzsch esters (or nitrile) as radical alkylation reagents. Notably, the α-C(sp(3))-H of tertiary amines can be directly alkylated to form the C(sp(3))-C(sp(3)) bonds via C(sp(3))-H − C(sp(3))-H cross coupling through the same photoredox pathway. Nature Publishing Group UK 2020-03-19 /pmc/articles/PMC7081228/ /pubmed/32193371 http://dx.doi.org/10.1038/s41467-020-15167-2 Text en © The Author(s) 2020 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/.
spellingShingle Article
Guo, Quanping
Peng, Qiang
Chai, Hongli
Huo, Yumei
Wang, Shan
Xu, Zhaoqing
Visible-light promoted regioselective amination and alkylation of remote C(sp(3))-H bonds
title Visible-light promoted regioselective amination and alkylation of remote C(sp(3))-H bonds
title_full Visible-light promoted regioselective amination and alkylation of remote C(sp(3))-H bonds
title_fullStr Visible-light promoted regioselective amination and alkylation of remote C(sp(3))-H bonds
title_full_unstemmed Visible-light promoted regioselective amination and alkylation of remote C(sp(3))-H bonds
title_short Visible-light promoted regioselective amination and alkylation of remote C(sp(3))-H bonds
title_sort visible-light promoted regioselective amination and alkylation of remote c(sp(3))-h bonds
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7081228/
https://www.ncbi.nlm.nih.gov/pubmed/32193371
http://dx.doi.org/10.1038/s41467-020-15167-2
work_keys_str_mv AT guoquanping visiblelightpromotedregioselectiveaminationandalkylationofremotecsp3hbonds
AT pengqiang visiblelightpromotedregioselectiveaminationandalkylationofremotecsp3hbonds
AT chaihongli visiblelightpromotedregioselectiveaminationandalkylationofremotecsp3hbonds
AT huoyumei visiblelightpromotedregioselectiveaminationandalkylationofremotecsp3hbonds
AT wangshan visiblelightpromotedregioselectiveaminationandalkylationofremotecsp3hbonds
AT xuzhaoqing visiblelightpromotedregioselectiveaminationandalkylationofremotecsp3hbonds