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Total Synthesis of Shearinines D and G: A Convergent Approach to Indole Diterpenoids
The first total syntheses of the indole diterpenoids (+)‐shearinine G and D are disclosed. The successful routes rely on late‐stage coupling of two complex fragments. Formation of the challenging trans‐hydrindane motif was accomplished by diastereoselective, intramolecular cyclopropanation. A one‐po...
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/PMC9300186/ https://www.ncbi.nlm.nih.gov/pubmed/34738695 http://dx.doi.org/10.1002/anie.202112838 |
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author | Hauser, Nicole Imhof, Michael A. Eichenberger, Sarah S. Kündig, Tomas Carreira, Erick M. |
author_facet | Hauser, Nicole Imhof, Michael A. Eichenberger, Sarah S. Kündig, Tomas Carreira, Erick M. |
author_sort | Hauser, Nicole |
collection | PubMed |
description | The first total syntheses of the indole diterpenoids (+)‐shearinine G and D are disclosed. The successful routes rely on late‐stage coupling of two complex fragments. Formation of the challenging trans‐hydrindane motif was accomplished by diastereoselective, intramolecular cyclopropanation. A one‐pot sequence consisting of Sharpless dihydroxylation/Achmatowicz reaction was developed to install the dioxabicyclo[3.2.1]octane motif. The indenone subunit was accessed by Prins cyclization. Tuning the electronic nature of the substituents on the parent arylcarboxaldehyde allowed access to divergent products that were further transformed into shearinines G and D. Riley‐type oxidation of a bicyclic enone yielded a surprising stereochemical outcome. |
format | Online Article Text |
id | pubmed-9300186 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-93001862022-07-21 Total Synthesis of Shearinines D and G: A Convergent Approach to Indole Diterpenoids Hauser, Nicole Imhof, Michael A. Eichenberger, Sarah S. Kündig, Tomas Carreira, Erick M. Angew Chem Int Ed Engl Research Articles The first total syntheses of the indole diterpenoids (+)‐shearinine G and D are disclosed. The successful routes rely on late‐stage coupling of two complex fragments. Formation of the challenging trans‐hydrindane motif was accomplished by diastereoselective, intramolecular cyclopropanation. A one‐pot sequence consisting of Sharpless dihydroxylation/Achmatowicz reaction was developed to install the dioxabicyclo[3.2.1]octane motif. The indenone subunit was accessed by Prins cyclization. Tuning the electronic nature of the substituents on the parent arylcarboxaldehyde allowed access to divergent products that were further transformed into shearinines G and D. Riley‐type oxidation of a bicyclic enone yielded a surprising stereochemical outcome. John Wiley and Sons Inc. 2021-12-09 2022-01-17 /pmc/articles/PMC9300186/ /pubmed/34738695 http://dx.doi.org/10.1002/anie.202112838 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 Hauser, Nicole Imhof, Michael A. Eichenberger, Sarah S. Kündig, Tomas Carreira, Erick M. Total Synthesis of Shearinines D and G: A Convergent Approach to Indole Diterpenoids |
title | Total Synthesis of Shearinines D and G: A Convergent Approach to Indole Diterpenoids |
title_full | Total Synthesis of Shearinines D and G: A Convergent Approach to Indole Diterpenoids |
title_fullStr | Total Synthesis of Shearinines D and G: A Convergent Approach to Indole Diterpenoids |
title_full_unstemmed | Total Synthesis of Shearinines D and G: A Convergent Approach to Indole Diterpenoids |
title_short | Total Synthesis of Shearinines D and G: A Convergent Approach to Indole Diterpenoids |
title_sort | total synthesis of shearinines d and g: a convergent approach to indole diterpenoids |
topic | Research Articles |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9300186/ https://www.ncbi.nlm.nih.gov/pubmed/34738695 http://dx.doi.org/10.1002/anie.202112838 |
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