A Simple and Efficient Method for the Partial Synthesis of Pure (3<i>R</i>,3’<i>S</i>)-Astaxanthin from (3<i>R</i>,3’<i>R</i>,6’<i>R</i>)-Lutein and Lutein Esters via (3<i>R</i>,3’<i>S</i>)-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...

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Main Authors: Eloy Rodríguez-deLeón, J. Oscar. C. Jiménez-Halla, José E. Báez, M. Moustapha Bah
Format: Article
Language:English
Published: MDPI AG 2019-04-01
Series:Molecules
Subjects:
Online Access:https://www.mdpi.com/1420-3049/24/7/1386
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spelling doaj-416cd822bb254744937e8b52100926962020-11-24T21:16:04ZengMDPI AGMolecules1420-30492019-04-01247138610.3390/molecules24071386molecules24071386A Simple and Efficient Method for the Partial Synthesis of Pure (3<i>R</i>,3’<i>S</i>)-Astaxanthin from (3<i>R</i>,3’<i>R</i>,6’<i>R</i>)-Lutein and Lutein Esters via (3<i>R</i>,3’<i>S</i>)-Zeaxanthin and Theoretical Study of Their Formation MechanismsEloy Rodríguez-deLeón0J. Oscar. C. Jiménez-Halla1José E. Báez2M. Moustapha Bah3Posgrado en Ciencias Químico Biológicas, Faculty of Chemistry, Autonomous University of Querétaro, Querétaro 76010, MexicoDepartment of Chemistry, Division of Natural and Exact Sciences, University of Guanajuato, Guanajuato 36050, MexicoDepartment of Chemistry, Division of Natural and Exact Sciences, University of Guanajuato, Guanajuato 36050, MexicoPosgrado en Ciencias Químico Biológicas, Faculty of Chemistry, Autonomous University of Querétaro, Querétaro 76010, MexicoCarotenoids 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 (3<i>R</i>,3&#8217;<i>R</i>,6&#8217;<i>R</i>)-lutein (<b>1</b>) esters has resulted in a successful isomerization process to easily obtain up to 95% meso-zeaxanthin (<b>2</b>), which in turn is oxidized to (3<i>R</i>,3&#8217;<i>S</i>)-astaxanthin (<b>3</b>) 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&#8217;, followed by C-4&#8217; protonation, while the oxidation occurs via free radical mechanisms.https://www.mdpi.com/1420-3049/24/7/1386carotenoids<i>meso</i>-zeaxanthin(3<i>R</i>,3’<i>S</i>)-astaxanthinpartial synthesisDFT calculationreaction mechanism
collection DOAJ
language English
format Article
sources DOAJ
author Eloy Rodríguez-deLeón
J. Oscar. C. Jiménez-Halla
José E. Báez
M. Moustapha Bah
spellingShingle Eloy Rodríguez-deLeón
J. Oscar. C. Jiménez-Halla
José E. Báez
M. Moustapha Bah
A Simple and Efficient Method for the Partial Synthesis of Pure (3<i>R</i>,3’<i>S</i>)-Astaxanthin from (3<i>R</i>,3’<i>R</i>,6’<i>R</i>)-Lutein and Lutein Esters via (3<i>R</i>,3’<i>S</i>)-Zeaxanthin and Theoretical Study of Their Formation Mechanisms
Molecules
carotenoids
<i>meso</i>-zeaxanthin
(3<i>R</i>,3’<i>S</i>)-astaxanthin
partial synthesis
DFT calculation
reaction mechanism
author_facet Eloy Rodríguez-deLeón
J. Oscar. C. Jiménez-Halla
José E. Báez
M. Moustapha Bah
author_sort Eloy Rodríguez-deLeón
title A Simple and Efficient Method for the Partial Synthesis of Pure (3<i>R</i>,3’<i>S</i>)-Astaxanthin from (3<i>R</i>,3’<i>R</i>,6’<i>R</i>)-Lutein and Lutein Esters via (3<i>R</i>,3’<i>S</i>)-Zeaxanthin and Theoretical Study of Their Formation Mechanisms
title_short A Simple and Efficient Method for the Partial Synthesis of Pure (3<i>R</i>,3’<i>S</i>)-Astaxanthin from (3<i>R</i>,3’<i>R</i>,6’<i>R</i>)-Lutein and Lutein Esters via (3<i>R</i>,3’<i>S</i>)-Zeaxanthin and Theoretical Study of Their Formation Mechanisms
title_full A Simple and Efficient Method for the Partial Synthesis of Pure (3<i>R</i>,3’<i>S</i>)-Astaxanthin from (3<i>R</i>,3’<i>R</i>,6’<i>R</i>)-Lutein and Lutein Esters via (3<i>R</i>,3’<i>S</i>)-Zeaxanthin and Theoretical Study of Their Formation Mechanisms
title_fullStr A Simple and Efficient Method for the Partial Synthesis of Pure (3<i>R</i>,3’<i>S</i>)-Astaxanthin from (3<i>R</i>,3’<i>R</i>,6’<i>R</i>)-Lutein and Lutein Esters via (3<i>R</i>,3’<i>S</i>)-Zeaxanthin and Theoretical Study of Their Formation Mechanisms
title_full_unstemmed A Simple and Efficient Method for the Partial Synthesis of Pure (3<i>R</i>,3’<i>S</i>)-Astaxanthin from (3<i>R</i>,3’<i>R</i>,6’<i>R</i>)-Lutein and Lutein Esters via (3<i>R</i>,3’<i>S</i>)-Zeaxanthin and Theoretical Study of Their Formation Mechanisms
title_sort simple and efficient method for the partial synthesis of pure (3<i>r</i>,3’<i>s</i>)-astaxanthin from (3<i>r</i>,3’<i>r</i>,6’<i>r</i>)-lutein and lutein esters via (3<i>r</i>,3’<i>s</i>)-zeaxanthin and theoretical study of their formation mechanisms
publisher MDPI AG
series Molecules
issn 1420-3049
publishDate 2019-04-01
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 (3<i>R</i>,3&#8217;<i>R</i>,6&#8217;<i>R</i>)-lutein (<b>1</b>) esters has resulted in a successful isomerization process to easily obtain up to 95% meso-zeaxanthin (<b>2</b>), which in turn is oxidized to (3<i>R</i>,3&#8217;<i>S</i>)-astaxanthin (<b>3</b>) 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&#8217;, followed by C-4&#8217; protonation, while the oxidation occurs via free radical mechanisms.
topic carotenoids
<i>meso</i>-zeaxanthin
(3<i>R</i>,3’<i>S</i>)-astaxanthin
partial synthesis
DFT calculation
reaction mechanism
url https://www.mdpi.com/1420-3049/24/7/1386
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