methyl 2,3-anhydro-4,6-di-O-benzyl-α-D-mannopyranoside | 146195-58-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,3-anhydro-4,6-di-O-benzyl-α-D-mannopyranoside
• 英文别名: (1S,2S,4R,5R,6S)-2-methoxy-5-phenylmethoxy-4-(phenylmethoxymethyl)-3,7-dioxabicyclo[4.1.0]heptane
• CAS: 146195-58-6
• 化学式: C₂₁H₂₄O₅
• 分子量: 356.419
• InChiKey: GBKGLTGBXHATDY-MJCUULBUSA-N

物化性质

• 沸点：
  482.6±45.0 °C(predicted)
• 密度：
  1.21±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  26
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  49.4
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 2,3-anhydro-4,6-di-O-benzyl-α-D-mannopyranoside 在 sodium azide 、 四乙基氯化铵 作用下， 以 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 168.0h， 以81%的产率得到
  参考文献：
  名称：

  Synthesis, crystalline structure, conformational analysis, and azidolysis of methyl 2,3-anhydro-α-d-manno- and -allo-pyranoside p-bromobenzyl

  摘要：

  Methyl 2,3-anhydro-4,6-di-O-p-bromobenzyl-alpha-D-allopyranoside (6) was synthesized from methyl 4,6-O-benzylidene-alpha-D-glucopyranoside (1) via the intermediate methyl 4,6-di-O-p-bromobenzyl-2,3-di-O-p-tolylsulfonyl-alpha-D-glucopyranoside. Treatment of 6 with sodium azide selectively afforded methyl 3-azido-4,6-di-O-p-bromobenzyl-3-deoxy-alpha-D-glucopyranoside in 70% yield. Methyl 2,3-anhydro-4,6-di-O-p-bromobenzyl-(17) and methyl 2,3-anhydro-4,6-di-O-benzyl-alpha-D-mannopyranoside (18) were obtained from 1 via the intermediates methyl 4,6-di-O-p-bromobenzyl- and methyl 4,6-di-O-benzyl-2-O-p-tolylsulfonyl-alpha-D-glucopyranoside. Azidolysis of 17 and 18 with sodium azide in the presence of tetraethylammonium chloride in N,N-dimethylformamide gave the respective 3-azidoaltropyransides, in yields of 80%, by exclusive 3-attack. The crystal structure of compound 6 is orthorhombic with a space group of P2(1)2(1)2(1), and the 2,3-anhydropyranose moiety is in an almost ideal degrees-H-5 half-chair conformation. The crystals of 17 are also orthorhombic, belonging to space group P2(1)2(1)2(1), but the conformation is a hybrid of the degrees-H-5 half-chair and the degrees-E sofa. Analysis by NMR spectroscopy suggests that in solution in CDCl3 the conformation of 17 remains the same as, and that of 6 undergoes a change from, the respective solid-state conformations.

  DOI：

  10.1016/0008-6215(92)80086-g
• 作为产物：
  描述：

  methyl 4,6-di-O-benzyl-2-O-p-tolylsulfonyl-α-D-glucopyranoside 在 sodium methylate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 0.33h， 以85%的产率得到methyl 2,3-anhydro-4,6-di-O-benzyl-α-D-mannopyranoside
  参考文献：
  名称：

  Synthesis, crystalline structure, conformational analysis, and azidolysis of methyl 2,3-anhydro-α-d-manno- and -allo-pyranoside p-bromobenzyl

  摘要：

  Methyl 2,3-anhydro-4,6-di-O-p-bromobenzyl-alpha-D-allopyranoside (6) was synthesized from methyl 4,6-O-benzylidene-alpha-D-glucopyranoside (1) via the intermediate methyl 4,6-di-O-p-bromobenzyl-2,3-di-O-p-tolylsulfonyl-alpha-D-glucopyranoside. Treatment of 6 with sodium azide selectively afforded methyl 3-azido-4,6-di-O-p-bromobenzyl-3-deoxy-alpha-D-glucopyranoside in 70% yield. Methyl 2,3-anhydro-4,6-di-O-p-bromobenzyl-(17) and methyl 2,3-anhydro-4,6-di-O-benzyl-alpha-D-mannopyranoside (18) were obtained from 1 via the intermediates methyl 4,6-di-O-p-bromobenzyl- and methyl 4,6-di-O-benzyl-2-O-p-tolylsulfonyl-alpha-D-glucopyranoside. Azidolysis of 17 and 18 with sodium azide in the presence of tetraethylammonium chloride in N,N-dimethylformamide gave the respective 3-azidoaltropyransides, in yields of 80%, by exclusive 3-attack. The crystal structure of compound 6 is orthorhombic with a space group of P2(1)2(1)2(1), and the 2,3-anhydropyranose moiety is in an almost ideal degrees-H-5 half-chair conformation. The crystals of 17 are also orthorhombic, belonging to space group P2(1)2(1)2(1), but the conformation is a hybrid of the degrees-H-5 half-chair and the degrees-E sofa. Analysis by NMR spectroscopy suggests that in solution in CDCl3 the conformation of 17 remains the same as, and that of 6 undergoes a change from, the respective solid-state conformations.

  DOI：

  10.1016/0008-6215(92)80086-g

文献信息

• Synthesis of carbasugar-containing non-glycosidically linked pseudodisaccharides and higher pseudooligosaccharides
  作者：Ian Cumpstey

  DOI：10.1016/j.carres.2009.09.008

  日期：2009.11

  This minireview covers synthetic methods towards carbasugar-containing non-glycosidically linked pseudodisaccharides or higher pseudooligosaccharides. Carbocyclic pyranose mimetics (saturated or unsaturated between C-5 and C-5a) are linked by ether, thioether or amine bridges to carbohydrates or other carbasugars.

  这份简短的综述涵盖了针对含碳水化合物的非糖苷键连接的假二糖或高级假寡糖的合成方法。碳环吡喃糖模拟物（在C-5和C-5a之间饱和或不饱和）通过醚桥，硫醚桥或胺桥连接到碳水化合物或其他Carcarbugars。
• Synthesis of Ether-Linked Sugar by Nucleophilic Opening of Carbohydrate Oxiranes
  作者：Hideyo Takahashi、Kazusa Nishiyama、Takahiro Nakayama、Hideaki Natsugari

  DOI：10.1055/s-0028-1083221

  日期：2008.12

  A new synthesis of ether-linked sugar utilizing the nucleophilic ring-opening reaction of carbohydrate α- or β-oxirane was developed. The reaction of 2,3-anhydro-α-d-mannopyranosides resulted in the expected high regioselectivity. In contrast, 2,3-anhydro-α-d-allopyranosides showed an unusual regioselectivity shift. The differentiating properties of carbohydrate α- or β-oxirane were investigated by comparing various conditions of the reaction.

  开发了一种利用糖类α-或β-氧环的亲核开环反应合成醚连接糖的新方法。2,3-脱水-α-d-甘露糖苷的反应产生了预期的高区位选择性。相反，2,3-脱水-α-d-阿洛糖苷则表现出不寻常的区位选择性转变。通过比较不同反应条件，研究了糖类α-或β-氧环的区分特性。
• Synthesis of α-glucosidase inhibitors: kojibiose-type pseudodisaccharides and a related pseudotrisaccharide11Pseudosugars, Part 38: For Part 37, see ref.[1].
  作者：Seiichiro Ogawa、Makoto Ashiura、Chikara Uchida

  DOI：10.1016/s0008-6215(98)00045-7

  日期：1998.2

  nitrogen bridges to the sugar residues, have been designed and synthesized as processing α -glucosidase I inhibitors. Synthesis of the pseudodisaccharides was carried out starting from the coupling products of the sugar isothiocyanates and an aminocyclitol, respectively, by cyclization with mercury(II) oxide to the cyclic isoureas and subsequent deprotection. Pseudokojibiose was prepared in a poor yield

  摘要设计并合成了两种曲霉二糖型假二糖和一种三糖，它们含有5-氨基-1,2,3,4-环戊netetrol衍生物或缬氨酸胺，它们通过氮桥与糖残基连接，并作为加工α合成。 -葡糖苷酶I抑制剂。假二糖的合成分别从糖异硫氰酸酯和氨基环糖醇的偶联产物开始，通过用氧化汞（II）环化成环状异脲并随后脱保护来进行。通过保护的瓦伦胺和糖环氧化物的反应，然后脱保护，制备伪假二糖的收率很低。尽管拟低聚糖都是α-葡萄糖苷酶（面包酵母）的强抑制剂，
• 1,1-Dioxothiomorpholines with asymmetric environments: protecting group directed diastereoselectivity of glyco divinyl sulfone cyclization
  作者：Atanu Bhaumik、Tarun Kumar Pal、Tanmaya Pathak

  DOI：10.1039/c5ra03276h

  日期：——

  afforded 1,1-dioxothiomorpholine with predefined asymmetric environments. Although the exocyclic vinyl sulfone group easily reacts with primary amines, the intramolecular addition pattern of the secondary amine leading to the formation of the 1,1-dioxothiomorpholine derivative dramatically varied when benzylidene protection was replaced by benzyl protecting groups.

  从吡喃糖苷骨架衍生的二乙烯基砜提供了具有预定义的不对称环境的1，1-二氧代硫吗啉。尽管环外乙烯基砜基团容易与伯胺反应，但是当用亚苄基保护基团代替亚苄基保护基时，导致形成1，1-二氧代硫代吗啉衍生物的仲胺的分子内加成模式发生了巨大变化。
• Novel Glycosidation of α-d-Altropyranosides
  作者：Hideyo Takahashi、Takahiro Nakayama、Kazusa Nishiyama、Hideaki Natsugari

  DOI：10.1055/s-0029-1217073

  日期：2010.1

  A new glycosidation of α-d-altropyranosides, in which the 2-hydroxy group is not protected, was developed. The reaction proceeds via a 1,2-β-oxirane, which is formed in situ without extra steps for exchanging the 1-methoxy group to a more reactive leaving group. The glycoside bond of α-d-altropyranoside was shown to be weaker compared with those of α-d-glucopyranoside and α-d-mannopyranoside.

  研究人员开发了一种新的δ-d-altropyranosides糖苷化反应，其中 2-羟基不受保护。反应通过 1,2-δ-环氧乙烷进行，该环氧乙烷在原位形成，无需额外步骤将 1-甲氧基交换为活性更强的离去基团。与δ-d-吡喃葡萄糖苷和δ-d-吡喃甘露糖苷相比，δ-d-阿洛糖苷的苷键较弱。