1,6-anhydro-4-O-benzyl-2,3-dideoxy-2,3-epimino-β-D-allopyranose | 101024-16-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1,6-anhydro-4-O-benzyl-2,3-dideoxy-2,3-epimino-β-D-allopyranose
• 英文别名: (1R,2R,4S,5S,6R)-5-phenylmethoxy-8,9-dioxa-3-azatricyclo[4.2.1.02,4]nonane
• CAS: 101024-16-2
• 化学式: C₁₃H₁₅NO₃
• 分子量: 233.267
• InChiKey: VAFLXWFQXHPGID-NZEXEKPDSA-N

物化性质

• 沸点：
  359.5±42.0 °C(Predicted)
• 密度：
  1.30±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  49.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,6-anhydro-4-O-benzyl-2,3-dideoxy-2,3-epimino-β-D-allopyranose 在 氢溴酸 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 33.0h， 生成 1,6-anhydro-4-O-benzyl-3-bromo-2,3-dideoxy-2-(N-o-nitrobenzenesulfonylamino)-β-D-glucopyranose
  参考文献：
  名称：

  Utilization of nosylepimines of 1,6-anhydro-β-d-hexopyranoses for the preparation of halogenated aminosaccharides

  摘要：

  The aziridine ring cleavage of N-nosylepimines 3 and 7 having D-allo and D-manno configurations with halides led regioselectively to N-o-nitrobenzenesulfonylated 2-halo-3-amino- and 3-halo-2-amino-2,3-dideoxy derivatives of 1,6-anhydro-beta-D-glucopyranose 8-14 in 59-81% yields. Removal of o-nitrobenzenesulfonyl protecting group with benzenethiol afforded aminosaccharides, which were converted into more stable hydrochlorides 15-18. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2003.07.003
• 作为产物：
  描述：

  sodium ((1R,2S,3R,4R,5R)-2-(benzyloxy)-3-hydroxy-6,8-dioxabicyclo[3.2.1]octan-4-yl)carbamodithioate 在 吡啶 、 sodium hydroxide 、 碘 、 sodium methylate 作用下， 以 1,4-二氧六环 、 甲醇 、 乙醇 为溶剂， 反应 7.0h， 生成 1,6-anhydro-4-O-benzyl-2,3-dideoxy-2,3-epimino-β-D-allopyranose
  参考文献：
  名称：

  Elbert, Tomas; Cerny, Miloslav, Collection of Czechoslovak Chemical Communications, 1985, vol. 50, # 9, p. 2000 - 2009

  摘要：

  DOI：

文献信息

• Synthesis and NMR Spectra of 1,6-Anhydro-2,3-dideoxy-2,3-epimino- and 1,6-Anhydro-3,4-dideoxy-3,4-epimino-β-D-hexopyranoses
  作者：Jindřich Karban、Miloš Buděšínský、Miloslav Černý、Tomáš Trnka

  DOI：10.1135/cccc20010799

  日期：——

  A complete series of 2,3-dideoxy-2,3-epimino- and 3,4-dideoxy-3,4-epimino-1,6-anhydro-β-D-hexopyranoses were prepared by lithium aluminum hydride reduction of the corresponding trans-azido tosylates or trans-azido epoxides of 1,6-anhydro-β-D-hexopyranoses. The structure of the epimino derivatives was confirmed by ¹H and ¹³C NMR spectra.

  通过对应的trans-叔丁基磺酸酯或trans-叔丁基环氧化物的1,6-去水β-D-己糖吡喃的锂铝氢化还原，制备了一系列完整的2,3-二脱氧-2,3-环氨基和3,4-二脱氧-3,4-环氨基-1,6-去水β-D-己糖吡喃。环氨基衍生物的结构通过1H和13C NMR谱得到确认。
• Cleavage of the Epimines of 1,6-Anhydrohexoses with Fluoride Anion
  作者：Jiří Kroutil、Klára Jeništová

  DOI：10.1135/cccc20052075

  日期：——

  Aziridine ring cleavage reactions of five N-nosylepimines (2-6) having D-talo, D-galacto, D-manno, and D-allo configurations with potassium hydrogendifluoride under various reaction conditions have been performed. The cleavage regioselectively afforded diaxial isomers of vicinal amino-fluoro derivatives of 1,6-anhydro-β-D-gluco- and mannopyranose 7-11 in 51-94% yields. Removal of 2-nitrobenzenesulfonyl protecting group with benzenethiol has been attempted in the case of compound 10.

  对五种具有D-talo、D-galacto、D-manno和D-allo构型的N-烷基环丙胺（2-6）进行了钾氢二氟化物催化的环丙胺环开裂反应，在不同的反应条件下进行了实验。该开裂反应选择性地生成了1,6-脱水-β-D-葡萄和甘露糖衍生物的二轴异构体氨基-氟衍生物（7-11），产率为51-94%。在化合物10的情况下尝试了用苯硫醇去除2-硝基苯磺酰保护基。
• Aziridine Ring Cleavage by Nucleophiles in Epimino Derivatives of 1,6-Anhydro-β-D-hexopyranoses
  作者：Jiří Kroutil、Tomáš Trnka、Miloš Buděšínský、Miloslav Černý

  DOI：10.1002/1099-0690(200208)2002:15<2449::aid-ejoc2449>3.0.co;2-4

  日期：2002.8

  The regioselectivity of aziridine ring cleavage by nucleophiles (Cl−, Br−, I−, N3−, HBr) in a series of N-tosyl- and N-benzylepimino derivatives of 1,6-anhydro-β-D-hexopyranoses of D-allo, D-manno and D-galacto configurations has been studied. On treatment with halide anions, the tosylepimines 1, 3, 5 and 7 were opened trans-diaxially according to the Furst−Plattner rule. The courses of the reactions

  亲核试剂（Cl-、Br-、I-、N3-、HBr）在 D 的 1,6-脱水-β-D-吡喃己糖的一系列 N-tosyl- 和 N-benzylepimino 衍生物中对氮丙啶环裂解的区域选择性-allo、D-manno 和 D-galacto 构型已被研究。在用卤化物阴离子处理时，甲苯磺吡啶 1、3、5 和 7 根据 Furst-Plattner 规则经双轴打开。苄基亚胺 2、4、6 和 8 的反应过程在很大程度上取决于表亚胺的构型，部分取决于所用亲核试剂的类型。在用溴化物和碘化物处理时，D-allo（化合物 2、4）和 D-半乳糖（化合物 6）构型的 N-苄基亚胺产生跨赤道裂解产物，而甘露糖表亚胺 8 经双轴打开。相比下，所有苄基匹亚胺与叠氮化物和氢溴酸的反应都与构型无关，并且是反双轴进行的。(© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany,
• Elbert, Tomas; Cerny, Miloslav, Collection of Czechoslovak Chemical Communications, 1985, vol. 50, # 9, p. 2000 - 2009
  作者：Elbert, Tomas、Cerny, Miloslav

  DOI：——

  日期：——
• Utilization of nosylepimines of 1,6-anhydro-β-d-hexopyranoses for the preparation of halogenated aminosaccharides
  作者：Jiřı́ Kroutil、Jindřich Karban、Miloš Buděšı́nský

  DOI：10.1016/j.carres.2003.07.003

  日期：2003.11

  The aziridine ring cleavage of N-nosylepimines 3 and 7 having D-allo and D-manno configurations with halides led regioselectively to N-o-nitrobenzenesulfonylated 2-halo-3-amino- and 3-halo-2-amino-2,3-dideoxy derivatives of 1,6-anhydro-beta-D-glucopyranose 8-14 in 59-81% yields. Removal of o-nitrobenzenesulfonyl protecting group with benzenethiol afforded aminosaccharides, which were converted into more stable hydrochlorides 15-18. (C) 2003 Elsevier Ltd. All rights reserved.