Cargando…
A Simple and Efficient Method for the Partial Synthesis of Pure (3R,3’S)-Astaxanthin from (3R,3’R,6’R)-Lutein and Lutein Esters via (3R,3’S)-Zeaxanthin and Theoretical Study of Their Formation Mechanisms
Carotenoids are natural compounds that have important roles in promoting and maintaining human health. Synthetic astaxanthin is a highly requested product by the aquaculture industry, but natural astaxanthin is not. Various strategies have been developed to synthesize this carotenoid. Nonetheless, t...
Autores principales: | , , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2019
|
Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6480186/ https://www.ncbi.nlm.nih.gov/pubmed/30970551 http://dx.doi.org/10.3390/molecules24071386 |
_version_ | 1783413518276493312 |
---|---|
author | Rodríguez-deLeón, Eloy Jiménez-Halla, J. Oscar. C. Báez, José E. Bah, M. Moustapha |
author_facet | Rodríguez-deLeón, Eloy Jiménez-Halla, J. Oscar. C. Báez, José E. Bah, M. Moustapha |
author_sort | Rodríguez-deLeón, Eloy |
collection | PubMed |
description | Carotenoids are natural compounds that have important roles in promoting and maintaining human health. Synthetic astaxanthin is a highly requested product by the aquaculture industry, but natural astaxanthin is not. Various strategies have been developed to synthesize this carotenoid. Nonetheless, these approaches have not only provided limited global yields, but its main commercial source also carries several health risks for humans. In this contribution, the one-pot base-catalyzed reaction of (3R,3’R,6’R)-lutein (1) esters has resulted in a successful isomerization process to easily obtain up to 95% meso-zeaxanthin (2), which in turn is oxidized to (3R,3’S)-astaxanthin (3) with a global yield of 68%. The same oxidation performed with UV irradiation (365 nm) for 5 min provided the highest global yield (76%). These chemical transformations have also been achieved with a significant reduction of the health risks associated with its potential human consumption. Furthermore, this is the first time only one of the configurational isomers has been obtained semisynthetically. The poorly understood formation mechanisms of these two compounds were also investigated using Density-Functional Theory (DFT) calculations. These theoretical studies revealed that the isomerization involves a base-catalyzed deprotonation at C-6’, followed by C-4’ protonation, while the oxidation occurs via free radical mechanisms. |
format | Online Article Text |
id | pubmed-6480186 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-64801862019-04-30 A Simple and Efficient Method for the Partial Synthesis of Pure (3R,3’S)-Astaxanthin from (3R,3’R,6’R)-Lutein and Lutein Esters via (3R,3’S)-Zeaxanthin and Theoretical Study of Their Formation Mechanisms Rodríguez-deLeón, Eloy Jiménez-Halla, J. Oscar. C. Báez, José E. Bah, M. Moustapha Molecules Article Carotenoids are natural compounds that have important roles in promoting and maintaining human health. Synthetic astaxanthin is a highly requested product by the aquaculture industry, but natural astaxanthin is not. Various strategies have been developed to synthesize this carotenoid. Nonetheless, these approaches have not only provided limited global yields, but its main commercial source also carries several health risks for humans. In this contribution, the one-pot base-catalyzed reaction of (3R,3’R,6’R)-lutein (1) esters has resulted in a successful isomerization process to easily obtain up to 95% meso-zeaxanthin (2), which in turn is oxidized to (3R,3’S)-astaxanthin (3) with a global yield of 68%. The same oxidation performed with UV irradiation (365 nm) for 5 min provided the highest global yield (76%). These chemical transformations have also been achieved with a significant reduction of the health risks associated with its potential human consumption. Furthermore, this is the first time only one of the configurational isomers has been obtained semisynthetically. The poorly understood formation mechanisms of these two compounds were also investigated using Density-Functional Theory (DFT) calculations. These theoretical studies revealed that the isomerization involves a base-catalyzed deprotonation at C-6’, followed by C-4’ protonation, while the oxidation occurs via free radical mechanisms. MDPI 2019-04-09 /pmc/articles/PMC6480186/ /pubmed/30970551 http://dx.doi.org/10.3390/molecules24071386 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 Rodríguez-deLeón, Eloy Jiménez-Halla, J. Oscar. C. Báez, José E. Bah, M. Moustapha A Simple and Efficient Method for the Partial Synthesis of Pure (3R,3’S)-Astaxanthin from (3R,3’R,6’R)-Lutein and Lutein Esters via (3R,3’S)-Zeaxanthin and Theoretical Study of Their Formation Mechanisms |
title | A Simple and Efficient Method for the Partial Synthesis of Pure (3R,3’S)-Astaxanthin from (3R,3’R,6’R)-Lutein and Lutein Esters via (3R,3’S)-Zeaxanthin and Theoretical Study of Their Formation Mechanisms |
title_full | A Simple and Efficient Method for the Partial Synthesis of Pure (3R,3’S)-Astaxanthin from (3R,3’R,6’R)-Lutein and Lutein Esters via (3R,3’S)-Zeaxanthin and Theoretical Study of Their Formation Mechanisms |
title_fullStr | A Simple and Efficient Method for the Partial Synthesis of Pure (3R,3’S)-Astaxanthin from (3R,3’R,6’R)-Lutein and Lutein Esters via (3R,3’S)-Zeaxanthin and Theoretical Study of Their Formation Mechanisms |
title_full_unstemmed | A Simple and Efficient Method for the Partial Synthesis of Pure (3R,3’S)-Astaxanthin from (3R,3’R,6’R)-Lutein and Lutein Esters via (3R,3’S)-Zeaxanthin and Theoretical Study of Their Formation Mechanisms |
title_short | A Simple and Efficient Method for the Partial Synthesis of Pure (3R,3’S)-Astaxanthin from (3R,3’R,6’R)-Lutein and Lutein Esters via (3R,3’S)-Zeaxanthin and Theoretical Study of Their Formation Mechanisms |
title_sort | simple and efficient method for the partial synthesis of pure (3r,3’s)-astaxanthin from (3r,3’r,6’r)-lutein and lutein esters via (3r,3’s)-zeaxanthin and theoretical study of their formation mechanisms |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6480186/ https://www.ncbi.nlm.nih.gov/pubmed/30970551 http://dx.doi.org/10.3390/molecules24071386 |
work_keys_str_mv | AT rodriguezdeleoneloy asimpleandefficientmethodforthepartialsynthesisofpure3r3sastaxanthinfrom3r3r6rluteinandluteinestersvia3r3szeaxanthinandtheoreticalstudyoftheirformationmechanisms AT jimenezhallajoscarc asimpleandefficientmethodforthepartialsynthesisofpure3r3sastaxanthinfrom3r3r6rluteinandluteinestersvia3r3szeaxanthinandtheoreticalstudyoftheirformationmechanisms AT baezjosee asimpleandefficientmethodforthepartialsynthesisofpure3r3sastaxanthinfrom3r3r6rluteinandluteinestersvia3r3szeaxanthinandtheoreticalstudyoftheirformationmechanisms AT bahmmoustapha asimpleandefficientmethodforthepartialsynthesisofpure3r3sastaxanthinfrom3r3r6rluteinandluteinestersvia3r3szeaxanthinandtheoreticalstudyoftheirformationmechanisms AT rodriguezdeleoneloy simpleandefficientmethodforthepartialsynthesisofpure3r3sastaxanthinfrom3r3r6rluteinandluteinestersvia3r3szeaxanthinandtheoreticalstudyoftheirformationmechanisms AT jimenezhallajoscarc simpleandefficientmethodforthepartialsynthesisofpure3r3sastaxanthinfrom3r3r6rluteinandluteinestersvia3r3szeaxanthinandtheoreticalstudyoftheirformationmechanisms AT baezjosee simpleandefficientmethodforthepartialsynthesisofpure3r3sastaxanthinfrom3r3r6rluteinandluteinestersvia3r3szeaxanthinandtheoreticalstudyoftheirformationmechanisms AT bahmmoustapha simpleandefficientmethodforthepartialsynthesisofpure3r3sastaxanthinfrom3r3r6rluteinandluteinestersvia3r3szeaxanthinandtheoreticalstudyoftheirformationmechanisms |