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Stereocontrolled Total Synthesis of (−)‐Stemaphylline
Homologation of readily available α‐boryl pyrrolidines with metal carbenoids is especially challenging even when good leaving groups (Cl(−)) are employed. By performing a solvent switch from Et(2)O to CHCl(3), efficient 1,2‐metalate rearrangement of the intermediate boronate occurs with both halide...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2017
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5484348/ https://www.ncbi.nlm.nih.gov/pubmed/28097799 http://dx.doi.org/10.1002/anie.201611273 |
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author | Varela, Ana Garve, Lennart K. B. Leonori, Daniele Aggarwal, Varinder K. |
author_facet | Varela, Ana Garve, Lennart K. B. Leonori, Daniele Aggarwal, Varinder K. |
author_sort | Varela, Ana |
collection | PubMed |
description | Homologation of readily available α‐boryl pyrrolidines with metal carbenoids is especially challenging even when good leaving groups (Cl(−)) are employed. By performing a solvent switch from Et(2)O to CHCl(3), efficient 1,2‐metalate rearrangement of the intermediate boronate occurs with both halide and ester leaving groups. The methodology was used in the total synthesis of the Stemona alkaloid (−)‐stemaphylline in just 11 steps (longest linear sequence), with high stereocontrol (>20:1 d.r.) and 11 % overall yield. The synthesis also features a late‐stage lithiation–borylation reaction with a tertiary amine containing carbenoid. |
format | Online Article Text |
id | pubmed-5484348 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2017 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-54843482017-07-24 Stereocontrolled Total Synthesis of (−)‐Stemaphylline Varela, Ana Garve, Lennart K. B. Leonori, Daniele Aggarwal, Varinder K. Angew Chem Int Ed Engl Communications Homologation of readily available α‐boryl pyrrolidines with metal carbenoids is especially challenging even when good leaving groups (Cl(−)) are employed. By performing a solvent switch from Et(2)O to CHCl(3), efficient 1,2‐metalate rearrangement of the intermediate boronate occurs with both halide and ester leaving groups. The methodology was used in the total synthesis of the Stemona alkaloid (−)‐stemaphylline in just 11 steps (longest linear sequence), with high stereocontrol (>20:1 d.r.) and 11 % overall yield. The synthesis also features a late‐stage lithiation–borylation reaction with a tertiary amine containing carbenoid. John Wiley and Sons Inc. 2017-01-18 2017-02-13 /pmc/articles/PMC5484348/ /pubmed/28097799 http://dx.doi.org/10.1002/anie.201611273 Text en © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution (http://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
spellingShingle | Communications Varela, Ana Garve, Lennart K. B. Leonori, Daniele Aggarwal, Varinder K. Stereocontrolled Total Synthesis of (−)‐Stemaphylline |
title | Stereocontrolled Total Synthesis of (−)‐Stemaphylline |
title_full | Stereocontrolled Total Synthesis of (−)‐Stemaphylline |
title_fullStr | Stereocontrolled Total Synthesis of (−)‐Stemaphylline |
title_full_unstemmed | Stereocontrolled Total Synthesis of (−)‐Stemaphylline |
title_short | Stereocontrolled Total Synthesis of (−)‐Stemaphylline |
title_sort | stereocontrolled total synthesis of (−)‐stemaphylline |
topic | Communications |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5484348/ https://www.ncbi.nlm.nih.gov/pubmed/28097799 http://dx.doi.org/10.1002/anie.201611273 |
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