Animal carotenoids. 31. Structure elucidation of a sponge metabolite via mesylate elimination.
The structure of a sponge metabolite from Microciona prolifera, previously considered to be (6S)-2,3-didehydro- or 3,4-didehydro-gamma, chi-carotene, has been further studied. Attempted total synthesis of the 3,4-didehydro derivative provided the hitherto unknown gamma, chi-carotene, the synthesis of which is described. Hydrolysis of lutein methanesulfonate diester (dimesylate) gave elimination products possessing the 3,4-didehydro gamma end-group. 1H NMR data for this gamma end-group were identical with those for the sponge carotenoid. The mesylate elimination reaction described may mimic the metabolic formation of the 3,4-didehydro-gamma-carotenoid end-group. In connection with other investigations on functionalized carotenoids we further report the preparation of zeaxanthin and lutein mesylates and their base-catalyzed elimination reactions. SN2 type substitution reactions of zeaxanthin dimesylate with appropriate nucleophiles did not produce beta, beta-carotene, zeaxanthin diacetate or thiozeaxanthin.
Sliwka
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Nøkleby
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Liaaen-Jensen
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D000818:Animals; D002338:Carotenoids / Q000032:analysis* / Q000378:metabolism; D009682:Magnetic Resonance Spectroscopy; D008698:Mesylates / Q000032:analysis; D008968:Molecular Conformation; D011161:Porifera / Q000378:metabolism*
D008698:Mesylates; D002338:Carotenoids