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有机化学 ›› 2004, Vol. 24 ›› Issue (8): 946-949. 上一篇    下一篇

研究简报

一种新的保护的2-脱氧-2-氨基葡二糖合成

郭振楚*,a, 韩亮b, 胡博a, 曹赐生c   

  1. a湖南科技大学化学化工学院 湘潭 411201
    b南开大学元素有机化学研究所 天津 300071
    c湖南科技大学生命科学学院 湘潭 411201
  • 收稿日期:2003-06-30 修回日期:2004-02-28 接受日期:2004-02-28 发布日期:2022-09-20
  • 通讯作者: * E-mail: gzc0396@sina.com
  • 基金资助:
    湖南省“十五”有机化学重点学科(湘教通[2001]179号)资助项目.

Syntheses of New Protected 2-Deoxy-2-amino Diglucose

GUO Zhen-Chu*,a, HAN Liangb, HU Boa, CAO Ci-Shengc   

  1. aCollege of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201
    bResearch Institute of Elemento-organic Chemistry, Nankai University, Tianjin 300071
    cCollege of Life Science, Hunan University of Science and Technology, Xiangtan 411201
  • Received:2003-06-30 Revised:2004-02-28 Accepted:2004-02-28 Published:2022-09-20

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以氨基葡萄糖盐酸盐为原料制得糖基给体3,4,6-三-氧-乙酰-2-脱氧-2-(2,2,2-三氯乙氧)甲酰胺基-α-D-吡喃葡萄糖基三氯乙酰亚胺酯(5)和糖基受体烯丙基-4,6-氧-亚苄基-2-脱氧-2-(2,2,2-三氯乙氧)甲酰胺基-α-D-吡喃葡萄糖苷(7).在三甲基硅基三氟甲基磺酸酯(TMSOTf)条件下,给体5与受体7反应得到一种新的二糖烯丙基-3,4,6-三-氧-乙酰-2-脱氧-2-(2,2,2-三氯乙氧)甲酰胺基-β-D-吡喃葡萄糖-(1→3)-4,6-氧-亚苄基-2-脱氧-2-(2,2,2-三氯乙氧)甲酰胺基-α-D-吡喃葡萄糖糖苷(10),收率为39.2%.当7在无水BaO和Ba(OH)2·8H2O的条件下与BnBr进行3-OH苄基化反应时,却得到了烯丙基-3-氧-苄基-4,6-氧-亚苄基-2-脱氧-2-羟甲酰胺基-α-D-吡喃葡萄糖苷(8).改用Ag2O条件下与BnBr进行苄基化,得到预期的烯丙基-3-氧-苄基-4,6-氧-亚苄基-2-脱氧-2-(2,2,2-三氯乙氧)甲酰胺基-α-D-吡喃葡萄糖苷(9),从而避免了氨基保护基三氯乙氧甲酰基的水解.标题化合物10对枯草芽孢杆菌、葡伎根霉等微生物有一定的抑制作用.

关键词: 2-脱氧-2-氨基糖, 糖苷, 苄基化

The donor, 3,4,6-tri-O-acetyl-2-deoxy-2-(2,2,2-trichloroethoxy)carbonylamino-α-D-glucopyranosyl trichloroacetimidate (5), and the acceptor, allyl 4,6-O-benzylidene-2-deoxy-2-(2,2,2-trichloroethoxy)~carbonyl~amino-α-D-glucopyranoside (7), were prepared from D-glucosamine hydrochloride. Trichloroethoxycarbonyl group was used as an amino protecting group and trichloroacetimidate was used as aleaving group. Reaction of 5 with glycosylacceptor 7 in the presence of trimethylsilyl trifluoromethanesulfonateafforded the fully protected disaccharide allyl 3,4,6-tri-O-acetyl-2-deoxy-2-(2,2,2-trichloroethoxy)carbonylamino-β-D-glucopyranosyl-(1→3)-4,6-O-benzyl~idene-2-deoxy-2-(2,2,2-trichloroethoxy)carbonylamino-α-D-glucopyranoside (10) in yield of 39.2%. When 7 was treated with barium oxide, barium hydroxide octahydrate and benzyl bromide to realize benzylation at its 3-position, the unexpected product, allyl-3-O-benzyl-4,6-O-benzylidene-2-deoxy-2-hydroxy-carbonylamino-α-D-glucopyranoside (8), was obtained. But allyl-3-O-benzyl-4,6-O-benzylidene-2-deoxy-2-(2,2,2-trichloroethoxy)carbonylamino-α-D-glucopyranoside (9) was obtained smoothly without cleavage of the N-Troc in the benzylation of 3-hydroxyl group of 7 with BnBr in the presence of Ag2O. The title compound 10 has the moderate fungicidal activity to Bacillus subtilis and Rhizopus stolonifer et.

Key words: 2-amino-2-deoxy-glucose, glycoside, benzylation