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Switchable, Reagent‐Controlled Diastereodivergent Photocatalytic Carbocyclisation of Imine‐Derived α‐Amino Radicals
A reagent‐controlled stereodivergent carbocyclisation of aryl aldimine‐derived, photocatalytically generated, α‐amino radicals possessing adjacent conjugated alkenes, affording either bicyclic or tetracyclic products, is described. Under net reductive conditions using commercial Hantzsch ester, the...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8597041/ https://www.ncbi.nlm.nih.gov/pubmed/34449968 http://dx.doi.org/10.1002/anie.202107253 |
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author | Maitland, J. Andrew P. Leitch, Jamie A. Yamazaki, Ken Christensen, Kirsten E. Cassar, Doyle J. Hamlin, Trevor A. Dixon, Darren J. |
author_facet | Maitland, J. Andrew P. Leitch, Jamie A. Yamazaki, Ken Christensen, Kirsten E. Cassar, Doyle J. Hamlin, Trevor A. Dixon, Darren J. |
author_sort | Maitland, J. Andrew P. |
collection | PubMed |
description | A reagent‐controlled stereodivergent carbocyclisation of aryl aldimine‐derived, photocatalytically generated, α‐amino radicals possessing adjacent conjugated alkenes, affording either bicyclic or tetracyclic products, is described. Under net reductive conditions using commercial Hantzsch ester, the α‐amino radical species underwent a single stereoselective cyclisation to give trans‐configured amino‐indane structures in good yield, whereas using a substituted Hantzsch ester as a milder reductant afforded cis‐fused tetracyclic tetrahydroquinoline frameworks, resulting from two consecutive radical cyclisations. Judicious choice of the reaction conditions allowed libraries of both single and dual cyclisation products to be synthesised with high selectivity, notable predictability, and good‐to‐excellent yields. Computational analysis employing DFT revealed the reaction pathway and mechanistic rationale behind this finely balanced yet readily controlled photocatalytic system. |
format | Online Article Text |
id | pubmed-8597041 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-85970412021-11-22 Switchable, Reagent‐Controlled Diastereodivergent Photocatalytic Carbocyclisation of Imine‐Derived α‐Amino Radicals Maitland, J. Andrew P. Leitch, Jamie A. Yamazaki, Ken Christensen, Kirsten E. Cassar, Doyle J. Hamlin, Trevor A. Dixon, Darren J. Angew Chem Int Ed Engl Research Articles A reagent‐controlled stereodivergent carbocyclisation of aryl aldimine‐derived, photocatalytically generated, α‐amino radicals possessing adjacent conjugated alkenes, affording either bicyclic or tetracyclic products, is described. Under net reductive conditions using commercial Hantzsch ester, the α‐amino radical species underwent a single stereoselective cyclisation to give trans‐configured amino‐indane structures in good yield, whereas using a substituted Hantzsch ester as a milder reductant afforded cis‐fused tetracyclic tetrahydroquinoline frameworks, resulting from two consecutive radical cyclisations. Judicious choice of the reaction conditions allowed libraries of both single and dual cyclisation products to be synthesised with high selectivity, notable predictability, and good‐to‐excellent yields. Computational analysis employing DFT revealed the reaction pathway and mechanistic rationale behind this finely balanced yet readily controlled photocatalytic system. John Wiley and Sons Inc. 2021-10-13 2021-11-02 /pmc/articles/PMC8597041/ /pubmed/34449968 http://dx.doi.org/10.1002/anie.202107253 Text en © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH https://creativecommons.org/licenses/by/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
spellingShingle | Research Articles Maitland, J. Andrew P. Leitch, Jamie A. Yamazaki, Ken Christensen, Kirsten E. Cassar, Doyle J. Hamlin, Trevor A. Dixon, Darren J. Switchable, Reagent‐Controlled Diastereodivergent Photocatalytic Carbocyclisation of Imine‐Derived α‐Amino Radicals |
title | Switchable, Reagent‐Controlled Diastereodivergent Photocatalytic Carbocyclisation of Imine‐Derived α‐Amino Radicals |
title_full | Switchable, Reagent‐Controlled Diastereodivergent Photocatalytic Carbocyclisation of Imine‐Derived α‐Amino Radicals |
title_fullStr | Switchable, Reagent‐Controlled Diastereodivergent Photocatalytic Carbocyclisation of Imine‐Derived α‐Amino Radicals |
title_full_unstemmed | Switchable, Reagent‐Controlled Diastereodivergent Photocatalytic Carbocyclisation of Imine‐Derived α‐Amino Radicals |
title_short | Switchable, Reagent‐Controlled Diastereodivergent Photocatalytic Carbocyclisation of Imine‐Derived α‐Amino Radicals |
title_sort | switchable, reagent‐controlled diastereodivergent photocatalytic carbocyclisation of imine‐derived α‐amino radicals |
topic | Research Articles |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8597041/ https://www.ncbi.nlm.nih.gov/pubmed/34449968 http://dx.doi.org/10.1002/anie.202107253 |
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