Natural Occurrence of Enantiomeric and meso‐Astaxanthin 1. Ex Lobster Eggs (Homarus gammarus)

Rønneberg, Harald; Renstrøm, Britta; Aareskjold, Kåre; Liaaen‐Jensen, Synnøve; Vecchi, M.; Leuenberger, F. J.; Müller, Renate; Mayer, H.

doi:10.1002/hlca.19800630321

Cited by 52 publications

(3 citation statements)

References 17 publications

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“…Astaxanthin (3,3 0 -dihydroxy-,-carotene-4,4 0 -dione), AXT, shown schematically in Figs. 1(a)-(c), is a carotenoid occurring in nature as three optical isomers [3S,3 0 S, 3R,3 0 S, meso and 3R,3 0 R (SS, RS and RR) in various ratios; Rønneberg et al, 1980;Renstrøm et al, 1982]. It is present in shrimps, crabs and lobsters, as well as in many invertebrate animals, where interaction with a protein can cause the astaxanthin molecule to change its colour from an orange/red colour in the unbound form to a deep slate blue/black.…”

Section: Introductionmentioning

confidence: 99%

Unravelling the chemical basis of the bathochromic shift in the lobster carapace; new crystal structures of unbound astaxanthin, canthaxanthin and zeaxanthin

Bartalucci

Coppin

Fisher

et al. 2007

Acta Crystallogr Sect B

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The crystal structures of the unbound carotenoids, synthetic astaxanthin (3S,3'S:3R,3'S:3R,3'R in a 1:2:1 ratio), canthaxanthin and (3R,3'S, meso)-zeaxanthin are compared with each other and the protein bound astaxanthin molecule in the carotenoprotein, beta-crustacyanin. Three new crystal forms of astaxanthin have been obtained, using different crystallization conditions, comprising a chloroform solvate, a pyridine solvate and an unsolvated form. In each structure, the astaxanthin molecules, which are similar to one another, are centrosymmetric and adopt the 6-s-cis conformation; the end rings are bent out of the plane of the polyene chain by angles of -42.6 (5), -48.9 (5) and -50.4 (3) degrees , respectively, and are disordered, showing the presence of both R and S configurations (in a 1:1 ratio). In the crystal packing of the chloroform and pyridine solvates, the astaxanthin molecules show pair-wise end-to-end intermolecular hydrogen bonding of the adjacent 3-hydroxyl and 4-keto oxygens, whereas in the unsolvated crystal form, the hydrogen-bonding interaction is intermolecular. In addition, there are intermolecular C-H hydrogen bonds in all three structures. The canthaxanthin structure, measured at 100 and 293 K, also adopts the 6-s-cis conformation, but with disorder of one end ring only. The rotation of the end rings out of the plane of the polyene chains (ca -50 degrees for each structure) is similar to that of astaxanthin. A number of possible C-H hydrogen bonds to the keto O atoms are also observed. (3R,3'S, meso)-zeaxanthin is centrosymmetric with a C5-C6-C7-C8 torsion angle of -74.9 (3) degrees ; the molecules show pair-wise hydrogen bonding between the hydroxyl O atoms. In addition, for all the crystal structures the polyene chains were arranged one above the other, with intermolecular distances of 3.61-3.79 A, indicating the presence of pi-stacking interactions. Overall, these six crystal structures provide an ensemble of experimentally derived results that allow several key parameters, thought to influence colour tuning of the bathochromic shift of astaxanthin in crustacyanin, to be varied. The fact that the colour of each of the six crystals remains red, rather than turning blue, is therefore especially significant.

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Section: Introductionmentioning

confidence: 99%

Unravelling the chemical basis of the bathochromic shift in the lobster carapace; new crystal structures of unbound astaxanthin, canthaxanthin and zeaxanthin

Bartalucci

Coppin

Fisher

et al. 2007

Acta Crystallogr Sect B

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“…Sehr uberraschend waren daher neuere Befunde, die gezeigt haben, dass nicht nur das (S, S')-Isomere la, sondern alle optischen Isomeren dieses Carotinoides in der Natur vorkommen; so wurden z. B. aus Hummereiern alle optischen Isomeren des Astaxanthins isoliert [3]. Schon fruher war in einer Hefe (3R, 3'R)-Astaxanthin (le) aufgefunden worden [4].…”

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Technische Verfahren zur Synthese von Carotinoiden und verwandten Verbindungen aus Oxo‐isophoron. I. Modifizierung der Kienzle‐Mayer‐Synthese von (3S 3′S)‐Astaxanthin

Widmer

Zell

Lukac

et al. 1981

Helvetica Chimica Acta

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Technical Procedures for the Synthesis of Carotenoids and RelatedCompounds from 6-0x0-isophorone. I. Modification of the Kienzfe-Mayer-Synthesis of (3S, 3'S)-Astaxanthin SummaryAn efficient synthesis of (3S, 3's)-astaxanthin (la) in high yield and optical purity starting from (4R, 6R)-4-hydroxy-2,2,6-trimethylcyclohexanone (4) is reported. The absolute configuration of la, previously derived from ORD. data, has been confirmed by X-ray analysis of 5, a derivative of 6-0x0-isophorone (2). The key features of the improved synthesis are the two-step conversion of 4 to the key intermediate (4S)-2,6,6-trimethyl-4-hydroxy-2-cyclohexen-1-one (14), a new method for the partial reduction of the sterically hindered triple bond of (S)-6-hydroxy-3-(5-hydroxy-3-methyl-3-penten-l-ynyl)-2,4,4-trimethyl-2-cyclohexen-1-one (32), and Wittig olefination of the dialdehyde l,6-dimethyl-1,3, Soctatrienedial (38) using phosphonium salt 37 with a free hydroxyl group.

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“…Namely, astaxanthin in crustaceans and marine fishes exists as a mixture of three stereoisomers at C3 and C3′-positions [15,16]. Zeaxanthin [17], lutein [18], and tunaxanthin [19] in marine fishes also consist of these stereoisomers.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of (3S,3′S)- and meso-Stereoisomers of Alloxanthin and Determination of Absolute Configuration of Alloxanthin Isolated from Aquatic Animals

2014

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In order to determine the absolute configuration of naturally occurring alloxanthin, a HPLC analytical method for three stereoisomers 1a–c was established by using a chiral column. Two authentic samples, (3S,3′S)- and meso-stereoisomers 1b and 1c, were chemically synthesized according to the method previously developed for (3R,3′R)-alloxanthin (1a). Application of this method to various alloxanthin specimens of aquatic animals demonstrated that those isolated from shellfishes, tunicates, and crucian carp are identical with (3R,3′R)-stereoisomer 1a, and unexpectedly those from lake shrimp, catfish, biwa goby, and biwa trout are mixtures of three stereoisomers of 1a–c.

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Natural Occurrence of Enantiomeric and meso‐Astaxanthin 1. Ex Lobster Eggs (Homarus gammarus)

Cited by 52 publications

References 17 publications

Unravelling the chemical basis of the bathochromic shift in the lobster carapace; new crystal structures of unbound astaxanthin, canthaxanthin and zeaxanthin

Unravelling the chemical basis of the bathochromic shift in the lobster carapace; new crystal structures of unbound astaxanthin, canthaxanthin and zeaxanthin

Technische Verfahren zur Synthese von Carotinoiden und verwandten Verbindungen aus Oxo‐isophoron. I. Modifizierung der Kienzle‐Mayer‐Synthese von (3S 3′S)‐Astaxanthin

Synthesis of (3S,3′S)- and meso-Stereoisomers of Alloxanthin and Determination of Absolute Configuration of Alloxanthin Isolated from Aquatic Animals

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