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α-Branched amines through radical coupling with 2-azaallyl anions, redox active esters and alkenes
α-Branched amines are fundamental building blocks in a variety of natural products and pharmaceuticals. Herein is reported a unique cascade reaction that enables the preparation of α-branched amines bearing aryl or alkyl groups at the β- or γ-positions. The cascade is initiated by reduction of redox...
Autores principales: | , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2022
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8966660/ https://www.ncbi.nlm.nih.gov/pubmed/35432903 http://dx.doi.org/10.1039/d2sc00500j |
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author | Duan, Shengzu Zi, Yujin Wang, Lingling Cong, Jielun Chen, Wen Li, Minyan Zhang, Hongbin Yang, Xiaodong Walsh, Patrick J. |
author_facet | Duan, Shengzu Zi, Yujin Wang, Lingling Cong, Jielun Chen, Wen Li, Minyan Zhang, Hongbin Yang, Xiaodong Walsh, Patrick J. |
author_sort | Duan, Shengzu |
collection | PubMed |
description | α-Branched amines are fundamental building blocks in a variety of natural products and pharmaceuticals. Herein is reported a unique cascade reaction that enables the preparation of α-branched amines bearing aryl or alkyl groups at the β- or γ-positions. The cascade is initiated by reduction of redox active esters to alkyl radicals. The resulting alkyl radicals are trapped by styrene derivatives, leading to benzylic radicals. The persistent 2-azaallyl radicals and benzylic radicals are proposed to undergo a radical–radical coupling leading to functionalized amine products. Evidence is provided that the role of the nickel catalyst is to promote formation of the alkyl radical from the redox active ester and not promote the C–C bond formation. The synthetic method introduced herein tolerates a variety of imines and redox active esters, allowing for efficient construction of amine building blocks. |
format | Online Article Text |
id | pubmed-8966660 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-89666602022-04-14 α-Branched amines through radical coupling with 2-azaallyl anions, redox active esters and alkenes Duan, Shengzu Zi, Yujin Wang, Lingling Cong, Jielun Chen, Wen Li, Minyan Zhang, Hongbin Yang, Xiaodong Walsh, Patrick J. Chem Sci Chemistry α-Branched amines are fundamental building blocks in a variety of natural products and pharmaceuticals. Herein is reported a unique cascade reaction that enables the preparation of α-branched amines bearing aryl or alkyl groups at the β- or γ-positions. The cascade is initiated by reduction of redox active esters to alkyl radicals. The resulting alkyl radicals are trapped by styrene derivatives, leading to benzylic radicals. The persistent 2-azaallyl radicals and benzylic radicals are proposed to undergo a radical–radical coupling leading to functionalized amine products. Evidence is provided that the role of the nickel catalyst is to promote formation of the alkyl radical from the redox active ester and not promote the C–C bond formation. The synthetic method introduced herein tolerates a variety of imines and redox active esters, allowing for efficient construction of amine building blocks. The Royal Society of Chemistry 2022-03-03 /pmc/articles/PMC8966660/ /pubmed/35432903 http://dx.doi.org/10.1039/d2sc00500j Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/ |
spellingShingle | Chemistry Duan, Shengzu Zi, Yujin Wang, Lingling Cong, Jielun Chen, Wen Li, Minyan Zhang, Hongbin Yang, Xiaodong Walsh, Patrick J. α-Branched amines through radical coupling with 2-azaallyl anions, redox active esters and alkenes |
title | α-Branched amines through radical coupling with 2-azaallyl anions, redox active esters and alkenes |
title_full | α-Branched amines through radical coupling with 2-azaallyl anions, redox active esters and alkenes |
title_fullStr | α-Branched amines through radical coupling with 2-azaallyl anions, redox active esters and alkenes |
title_full_unstemmed | α-Branched amines through radical coupling with 2-azaallyl anions, redox active esters and alkenes |
title_short | α-Branched amines through radical coupling with 2-azaallyl anions, redox active esters and alkenes |
title_sort | α-branched amines through radical coupling with 2-azaallyl anions, redox active esters and alkenes |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8966660/ https://www.ncbi.nlm.nih.gov/pubmed/35432903 http://dx.doi.org/10.1039/d2sc00500j |
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