大豆异黄素7-O-2-乙酰氨基-2-脱氧-β-D-吡喃葡萄糖苷的合成
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摘要
以2-乙酰氨基葡萄糖为原料制得糖苷供体化合物1-氯-2-乙酰氨基-3,4,6-三-O-乙酰基-2-脱氧-α-D-吡喃葡萄糖,继续与大豆异黄素的7-位羟基经选择性糖苷化、脱乙酰化两步反应合成了7-O-2-乙酰氨基-2-脱氧-β-D-吡喃葡萄糖大豆异黄素苷。优化后的糖苷反应的最佳条件是:丙酮为反应溶剂,大豆异黄素、氯代糖和K_2CO_3的摩尔比1∶1.5∶1.5,反应温度为55℃,反应时间6 h,目标化合物总产率为64%,该化合物结构经NMR和HRMS确证,且水溶解度达到0.8mg·mL~(-1)。
2-Acetamido-3,4,6-tri-O-acetyl-2-deoxy-a-D-glucopyranosyl chloride wasobtained from 2-acetylglucosamine as a glycoside donor and its further selective glycosylation of C-7 hydroxyl groupof daidzein followed by deacetylation afforded 7-O-2-acetylamino-2-deoxy-β-D-glucopyranose-daidzein with the total of yield 64%.After optimization,glycosylation of daidzein was carried out at 55 ℃ in acetone for 6 h with a 1∶1.5∶1.5 molar ratio mixture of daidzein∶glycoside donor∶K_2CO_3.The structure of target compound was confirmed by NMR and HRMS and its solubility in water was 0.8 mg·mL~(-1).
2-Acetamido-3,4,6-tri-O-acetyl-2-deoxy-a-D-glucopyranosyl chloride wasobtained from 2-acetylglucosamine as a glycoside donor and its further selective glycosylation of C-7 hydroxyl groupof daidzein followed by deacetylation afforded 7-O-2-acetylamino-2-deoxy-β-D-glucopyranose-daidzein with the total of yield 64%.After optimization,glycosylation of daidzein was carried out at 55 ℃ in acetone for 6 h with a 1∶1.5∶1.5 molar ratio mixture of daidzein∶glycoside donor∶K_2CO_3.The structure of target compound was confirmed by NMR and HRMS and its solubility in water was 0.8 mg·mL~(-1).
引文
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[2]袁建平,王江海,刘昕.大豆异黄酮的重要代谢产物--马雌酚[J].中国药学杂志,2006,41(7):484-490.
[3]张家瑞,孙达亮,石娟娟,等.大豆黄素抗抑郁作用及其机制研究[J].中国新药杂志,2015,(13):1 531-1 536.
[4]肖咏梅,杨亮茹,邓玉霞,等.大豆苷元磷酰化改性及条件优化研究[J].粮食与油脂,2012,25(3):9-12.
[5]Soidinsalo O,Wahala K.Synthesis of daidzein 7-O-β-D-glucuronide-4′-O-sulfate[J].Steroids,2007,72(13):851-854.
[6]Lewis P,Kaltia S,Waehaelae K.The phase-transfer catalyzed synthesis of isoflavone-O-glucosides[J].Cheminform,1998,29(52):2 481-2 484.
[7]Mitsuyahongu,Kuniosaito,Kenjitsujihara.Solid-liquid phase transfer catalyzed novel glycosylation reaction of phenols[J].Cheminform,1999,29(16):2 775-2 781.
[8]郭瑞霞,冯俊霞,贾会珍,等.金雀异黄酮-4′-O糖苷的合成方法研究[J].河南化工,2013,30(7):36-38.
[9]Al-Maharik N,Botting N P.An efficient method for the glycosylation of isoflavones[J].Eur J Org Chem,2010,2008(33):5 622-5 629.
[10]Horton D.2-Acetamido-3,4,6-tri-O-acetyl-2-deoxy-α-D-glucopyranosyl chloride[J].Gen Carbohyd Meth,1972,6:282-285.
[11]Fan J P,Yang D,Xu X K,et al.Solubility of daidzin in different organic solvents and(ethyl alcohol+water)mixed solvents[J].J Chem Thermodyn,2015,88:85-89.