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Synthesis and Structural Determination of New Brassinosteroid 24-Nor-5α-Cholane Type Analogs

Natural brassinosteroids possess a 22R, 23R configuration that appears essential for biological activity. It is, therefore, interesting to elucidate if the activity of brassinosteroids with a short side chain depends on the C22 configuration. Herein, we describe the synthesis of new brassinosteroids...

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Autores principales: Oyarce, Jocelyn, Aitken, Vanessa, González, César, Ferrer, Karoll, Olea, Andrés F., Parella, Teodor, Espinoza Catalán, Luis
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2019
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6943489/
https://www.ncbi.nlm.nih.gov/pubmed/31861056
http://dx.doi.org/10.3390/molecules24244612
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author Oyarce, Jocelyn
Aitken, Vanessa
González, César
Ferrer, Karoll
Olea, Andrés F.
Parella, Teodor
Espinoza Catalán, Luis
author_facet Oyarce, Jocelyn
Aitken, Vanessa
González, César
Ferrer, Karoll
Olea, Andrés F.
Parella, Teodor
Espinoza Catalán, Luis
author_sort Oyarce, Jocelyn
collection PubMed
description Natural brassinosteroids possess a 22R, 23R configuration that appears essential for biological activity. It is, therefore, interesting to elucidate if the activity of brassinosteroids with a short side chain depends on the C22 configuration. Herein, we describe the synthesis of new brassinosteroids analogs with 24-norcholane type of side chain and R configuration at C22. The initial reaction is the dihydroxylation of a terminal olefin that leads to S/R epimers. Three different methods were tested in order to evaluate the obtained S/R ratio and the reaction yields. The results indicate that Upjohn dihydroxylation is the most selective reaction giving a 1.0:0.24 S/R ratio, whereas a Sharpless reaction leads to a mixture of 1.0:0.90 S/R with 95% yield. Using the latter mixture and following a previous reported method, benzoylated derivatives and both S and R brassinosteroids analogs were synthesized. All synthesized compounds were completely characterized by NMR spectroscopy, and HRMS of new compounds are also given. In conclusion, a synthetic route for preparation of new analogs of brassinosteroids of 24-norcholane type and R configuration at C22 were described. It is expected that this will help to elucidate if a configuration at C22 is a structural requirement for hormonal growth activity in plants.
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spelling pubmed-69434892020-01-10 Synthesis and Structural Determination of New Brassinosteroid 24-Nor-5α-Cholane Type Analogs Oyarce, Jocelyn Aitken, Vanessa González, César Ferrer, Karoll Olea, Andrés F. Parella, Teodor Espinoza Catalán, Luis Molecules Article Natural brassinosteroids possess a 22R, 23R configuration that appears essential for biological activity. It is, therefore, interesting to elucidate if the activity of brassinosteroids with a short side chain depends on the C22 configuration. Herein, we describe the synthesis of new brassinosteroids analogs with 24-norcholane type of side chain and R configuration at C22. The initial reaction is the dihydroxylation of a terminal olefin that leads to S/R epimers. Three different methods were tested in order to evaluate the obtained S/R ratio and the reaction yields. The results indicate that Upjohn dihydroxylation is the most selective reaction giving a 1.0:0.24 S/R ratio, whereas a Sharpless reaction leads to a mixture of 1.0:0.90 S/R with 95% yield. Using the latter mixture and following a previous reported method, benzoylated derivatives and both S and R brassinosteroids analogs were synthesized. All synthesized compounds were completely characterized by NMR spectroscopy, and HRMS of new compounds are also given. In conclusion, a synthetic route for preparation of new analogs of brassinosteroids of 24-norcholane type and R configuration at C22 were described. It is expected that this will help to elucidate if a configuration at C22 is a structural requirement for hormonal growth activity in plants. MDPI 2019-12-17 /pmc/articles/PMC6943489/ /pubmed/31861056 http://dx.doi.org/10.3390/molecules24244612 Text en © 2019 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Oyarce, Jocelyn
Aitken, Vanessa
González, César
Ferrer, Karoll
Olea, Andrés F.
Parella, Teodor
Espinoza Catalán, Luis
Synthesis and Structural Determination of New Brassinosteroid 24-Nor-5α-Cholane Type Analogs
title Synthesis and Structural Determination of New Brassinosteroid 24-Nor-5α-Cholane Type Analogs
title_full Synthesis and Structural Determination of New Brassinosteroid 24-Nor-5α-Cholane Type Analogs
title_fullStr Synthesis and Structural Determination of New Brassinosteroid 24-Nor-5α-Cholane Type Analogs
title_full_unstemmed Synthesis and Structural Determination of New Brassinosteroid 24-Nor-5α-Cholane Type Analogs
title_short Synthesis and Structural Determination of New Brassinosteroid 24-Nor-5α-Cholane Type Analogs
title_sort synthesis and structural determination of new brassinosteroid 24-nor-5α-cholane type analogs
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6943489/
https://www.ncbi.nlm.nih.gov/pubmed/31861056
http://dx.doi.org/10.3390/molecules24244612
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