Animal Carotenoids. 12. Chirality of Asterinic Acid.

Berger, Ragnar; Borch, Gunner; Liaaen‐Jensen, Synnøve; Söderholm, Anne-Charlotte; Undheim, Kjell; Berg, Jan-Erik; Pilotti, Anne‐Marie

doi:10.3891/acta.chem.scand.31b-0243

Cited by 22 publications

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“…Chromatographische Reinigung und Kristallisation aus Methylenchlorid/Methanol lieferte reines 21 . Die NMR.-Spektroskopie bewies die 9,9'-di- [5] Elektronen-, 1R.-, CD.-und Massenspektren des aus Asterias rubens isolierten, acetylierten Alkadiins stimmen gut uberein rnit den entsprechenden Spektren unseres synthetischen all-truns-Diacetats 33, hergestellt aus 1 rnit Acetanhydridl Pyridin bei 0". Ein diinnschichtchromatographischer Vergleich von 33 rnit einer aus Seestem isolierten Probe2) des acetylierten Alkadiins ergab identische Rf-Werte, welche sich eindeutig von demjenigen der cis-Isomeren 25 und 26 unterschieden.…”

Section: Discussionunclassified

“…Ein diinnschichtchromatographischer Vergleich von 33 rnit einer aus Seestem isolierten Probe2) des acetylierten Alkadiins ergab identische Rf-Werte, welche sich eindeutig von demjenigen der cis-Isomeren 25 und 26 unterschieden. Somit ist die vorgeschlagene absolute Konfiguration [5] der Hauptkomponenten der Asterinsaure, all-truns-(3S, 3'S) 8,7',, bestatigt. Fur die Synthese des naturlichen all-trans-Alkins 2 musste wiederum die umgekehrte Wittig-Reaktion angewandt werden.…”

Section: Discussionunclassified

“…Ein Vergleich der CD.-Kurven von synthetischem all-trans-(3R, 3'R)-Alloxanthin (4) [20], dessen 9,9'-di-cis-Isomeren [20], dem aus 1 durch Reduktion mit Natriumborhydrid synthetisierten all-trans-Tetrol49 (Diastereomerengemisch) und dem aus 21 erhaltenen 9,9'-di-cis-Tetrol50 (Diastereomerengemisch) ergab wie erwartet [ 5 ] annahernde Ubereinstimmung. Die fur all-trans-(3R, 3'R)-Diatoxanthin (5) veroffentlichte [26] CD.-Kurve stimmte gut mit derjenigen des aus 2 synthetisierten all-trans-Tetrols 51 (Diastereomerengemisch) uberein.…”

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“…-'H-NMR. (100 MHzr): 1,30 und 1,35 (2s, je 3 H, H3C(l6) und H3C(17)); 1,78(1, J, , ,= 12,5, 1 H, Ha,); 1,92 (s, 3 H, H3C(19)); 2, OO (s, 3 H, H3C(l8)); 2,22 (dxd, J,,,= 12,5, J2,3=5,7, 1 H, H-C(2)). -l3C-NMR (22,…”

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Synthese von optisch aktiven, natürlichen Carotinoiden und strukturell verwandten Naturprodukten. VIII. Synthese von (3S,3′S)‐7,8,7′,8′‐Tetradehydroastaxanthin und (3S,3′S)‐7,8‐Didehydroastaxanthin (Asterinsäure)

Bernhard

Kienzle

Mayer

et al. 1980

Helvetica Chimica Acta

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Synthesis of Optically Active Natural Carotenoids and Structurally Related Compounds. VIII. Synthesis of (3S,3′S)‐7,8,7′,8′‐Tetradehydroastaxanthin and (3S,3′S)‐7,8‐Didehydroastaxanthin (Asterinic Acid) The synthesis of all‐trans‐(3S,3′S)‐3,3′‐dihydroxy‐7,8, 7′,8′‐tetradehydro‐β, β‐carotene‐4,4′‐dione (1), of all‐trans‐(3S,3′S)‐3,3′‐dihydroxy‐7, 8‐didehydro‐β,β‐carotene‐4,4′‐dione (2) (asterinic acid = mixture of 1 and 2), and of their 9,9′‐di‐cis‐ and 9‐cis‐isomers is reported starting from (4′S)(2E)‐5‐(4′‐hydroxy‐2′, 6′,6′‐trimethyl‐3′‐oxo‐l′‐cyclohexenyl)‐3‐methyl‐2‐penten‐4‐ynal (8). The absolute configuration (3S,3′S) for both components 1 and 2 of asterinic acid ex Asterias rubens is confirmed on the basis of spectroscopic and direct comparison.

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Section: Discussionunclassified

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Synthese von optisch aktiven, natürlichen Carotinoiden und strukturell verwandten Naturprodukten. VIII. Synthese von (3S,3′S)‐7,8,7′,8′‐Tetradehydroastaxanthin und (3S,3′S)‐7,8‐Didehydroastaxanthin (Asterinsäure)

Bernhard

Kienzle

Mayer

et al. 1980

Helvetica Chimica Acta

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“…the corresponding tetrols with (3 R , 3'R)-alloxanthin (4a) and (3 R, 3'R)-diatoxanthin (Sa), respectively [6], subsequently confirmed by total syntheses of the pure all-trans-(3 S , 3'S)-isomers 2a and 3a [ 161. Recently, also the 9,9'-di-cis-isomers of 3,3a and 3c have been prepared by total syntheses [17].…”

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Carotenoids of the Carotenoprotein Asteriarubin. Optical Purity of Asterinic Acid

Bernhard

Englert

Meister

et al. 1982

Helvetica Chimica Acta

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The carotenoid composition of the carotenoprotein asteriarubin ex the starfish Asterias rubens, determined by HPLC, comprised canthaxanthin (6, 3% of total), all‐trans‐astaxanthin (1, 14%), all‐trans‐7,8‐didehydroastaxanthin (2, 24%), all‐trans‐7,8,7′,8′‐tetradehydroastaxanthin (3, 43%) and 4‐oxomytiloxanthin (7, 10%). The previously unknown 4‐oxomytiloxanthin was tentatively identified by the UV./VIS., 'H‐NMR. spectra and MS. data. The optical purity was determined by HPLC. of the di‐(−)‐camphanates, by comparison with those of synthetic standards: 7,8,7′, 8′‐tetradehydroastaxanthin (92% (3S, 3′S), 2% meso), 7,8‐didehydroastaxanthin (89% (3S,3′S), 2% meso?), and astaxanthin (78% (3S,3′S), 14% (3R,3′S), and 5% (3R,3′R)). It is concluded that the acetylenic derivatives of astaxanthin in contrast to astaxanthin from marine animal sources are essentially pure (3S, 3′S)‐isomers. This might reflect their probable metabolic formation by 4‐oxo modification of acetylenic (3R,3′R)‐carotenols ex Mytilus edulis in their diet.

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