Carotinoid‐Glycosylester 4. Mitteilung. Synthese von 8′‐Apo‐β‐carotin‐8′‐säure‐(β‐<scp>D</scp>‐glucosyl)ester und Vitamin‐A‐säure‐(β‐<scp>D</scp>‐glucosyl)ester

The toxic and teratogenic effects caused by the highly biolo-synthesized under Koenigs-Knorr conditions from (all-E)-retigically active (all-E)-retinoic acid and its derivatives n&l and an a-halogenose. Compounds 5 and 8 were prepared prompted us to synthesize a number of retinoids. We develo-by esterification of a silver salt of (all-E)-retinoic acid with an ped synthetic approaches to (all-E)-retinyl p-D-glucuronide 3, a-glycosyl halide in pyridine. (all-E)-Retinoyl P-D-glucuromethyl (retinoyl p-D-g1ucopyranoside)uronate 5, (all-E)-reti-nide 6 was prepared by reaction of (all-E)-retinoyl fluoride noic acid P-D-glucopyranosyl ester 8 and (all-E)-retinoyl p-with underivatized P-D-glucuronic acid. Compounds 5,6 and D-glucuronide 6 in high purity and yield. Compound 3 was 8 show biological effects similiar to those of retinoic acid.Retinol, retinoic acid and their derivatives are involved in processes of controlling growth and differentiation of normal and neoplastic cells through interaction with a nuclear receptor. In addition to the high biological activity, toxicity and teratogenic effects of retinoic acid and some of it's derivatives, it is known that there are problems arising in the application of these substances. New retinoids are to be synthesized, combining bioavailability in a wide range of aqueous cell compartments with a reduction of toxic and teratogenic effects.The synthesis of some polar and highly biologically active retinoAccording to well-known ~trategies[~-~] applied in the synthesis of (a/l-E)-retinyl pwglucuronide 3, (al/-E)-retinoic acid p-D-glUCOpyranosyl ester 8 and (all-E)-retinoyl p-D-ghcuronide 6 we optimized a variety of convenient methods, and obtained higher yields of the expected retinoids than previously reported. will be discussed. COOCH3 COOHThe synthesis of methyl (2,3,4-tri-O-acetyl-I-retinyl p-0-glucopyran0side)uronate 1 was carried out by reaction of (all-E)-retinol and an a-halogenose under Koenigs-Knorr conditions. The a-halogenose, 2,3,4-tn-O-acetyl-I -bromo-1 -deoxy-a-D-glucopyranuronic acid methyl ester, was obtained from D-( +)-glucofuranurono-3,6-lactone by alkaline cleavage of the lactone, protecting the carboxyl group as a methyl ester. The hydroxyl groups were deactivated by -4 5 6 7 8 R3 Acacetylation. The desired a-halogenose was then prepared by treatment of P-D-glucuronic acid methyl ester with HBr in glacial acetic acid.The Koenigs-Knorr reaction was best carried out by using silver trifluoromethanesulfonate as catalyst and 2,4,6-trimethylpyridine as the base. To obtain the desired P-product we used toluene as solvent and the reaction was carried out at low temperatures (-40°C) avoiding moisture, air, heat, light and acidic conditions. The desired product 1 was obtained in 72% yield. According to IH-and 13C-NMR data only a small amount of orthoester was detected.Deacetylation of 1 was preferably accomplished by using 0.1 N sodium methoxide in methanol to yield substance 2. The alkaline cleavage of the methyl ester of compound 2 was carried out by 1 N sodium hyd...

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Partial Synthesis of Glycosides and Glycosyl Esters

Pfander¹

1996

Carotenoids

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Carotinoid‐Glycosylester 4. Mitteilung. Synthese von 8′‐Apo‐β‐carotin‐8′‐säure‐(β‐D‐glucosyl)ester und Vitamin‐A‐säure‐(β‐D‐glucosyl)ester

Cited by 8 publications

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ChemInform Abstract: CAROTENOID GLYCOSYL ESTERS. PART 4. SYNTHESIS OF β‐D‐GLUCOSYL 8′‐APO‐β‐CAROTENE‐8′‐OATE AND β‐D‐GLUCOSYL VITAMIN‐A‐OATE

ChemInform Abstract: CAROTENOID GLYCOSYL ESTERS. PART 4. SYNTHESIS OF β‐D‐GLUCOSYL 8′‐APO‐β‐CAROTENE‐8′‐OATE AND β‐D‐GLUCOSYL VITAMIN‐A‐OATE

Convenient Synthesis of Biologically Important Retinoids

Partial Synthesis of Glycosides and Glycosyl Esters

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