2',3'-di-O-benzyl-α-D-glucopyranosyl 2,3-di-O-benzyl-4,6-O-benzylidene-α-D-glucopyranoside | 132294-63-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2',3'-di-O-benzyl-α-D-glucopyranosyl 2,3-di-O-benzyl-4,6-O-benzylidene-α-D-glucopyranoside
• 英文别名: (2R,3R,4S,5R,6R)-6-[[(2R,4aR,6R,7R,8S,8aR)-2-phenyl-7,8-bis(phenylmethoxy)-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-6-yl]oxy]-2-(hydroxymethyl)-4,5-bis(phenylmethoxy)oxan-3-ol
• CAS: 132294-63-4
• 化学式: C₄₇H₅₀O₁₁
• 分子量: 790.907
• InChiKey: KZFBLMHNFGJRJP-ABDVMWRRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  58
• 可旋转键数：
  16
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  124
• 氢给体数：
  2
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  2',3'-di-O-benzyl-α-D-glucopyranosyl 2,3-di-O-benzyl-4,6-O-benzylidene-α-D-glucopyranoside 在 palladium on activated charcoal 咪唑 、 氢气 、 碘 、 三乙胺 、 三苯基膦 作用下， 以 乙醇 、 甲苯 、 乙腈 为溶剂， 25.0~50.0 ℃ 、146.65 Pa 条件下， 反应 4.5h， 生成 2,3-Di-O-benzyl-6-deoxy-α-D-glucopyranosyl 2,3-di-O-benzyl-4,6-O-benzylidene-α-D-glucopyranoside
  参考文献：
  名称：

  Selectively Deoxygenated Derivatives of β-Maltosyl-(1→4)-Trehalose as Biological Probes

  摘要：

  The four derivatives of beta-maltosyl-(1 --> 4)-trehalose have been synthesized, which are monodeoxygenated at the site of one of the primary hydroxyl groups. The tetrasaccharides were constructed in [2+2] block syntheses. Thus, 6'''-deoxy-beta-maltosyl-(1 --> 4)-trehalose was prepared by selective iodination of allyl 2,3,6,2',3'-penta-O-acetyl-beta-maltoside (3) followed by catalytic hydrogenolysis and coupling with 2,3-di-O-benzyl-4,6-O-benzylidene-alpha-D-glucopyranosyl 2',3',6'-tri-O-benzyl-alpha-D-glucopyranoside (9), and 6 ''-deoxy-beta-maltosyl-(1 --> 4)-trehalose by selective iodination of allyl 4',6'-O-isopropylidene-beta-maltoside (14), coupling with 9, and one-step hydrogenolysis at the tetrasaccharide level. For the synthesis of 6'-deoxy-beta-maltosyl-(1 --> 4)-trehalose, the diol 2,3-di-O-benzyl-4,6-O-benzylidene-alpha-D-glucopyranosyl 2',3'-di-O-benzyl-alpha-D-glucopyranoside (22) was selectively iodinated and glycosylated with acetobromomaltose followed by catalytic hydrogenolysis. The 6-deoxy-beta-maltosyl-(1 --> 4)-trehalose was obtained upon selective iodination of a tetrasaccharide diol.

  DOI：

  10.1080/07328309608005672
• 作为产物：
  描述：

  2,3,2',3'-tetra-O-benzyl-4,6;4',6'-di-O-benzylidene-α,α-D-trehalose 在 二异丁基氢化铝 作用下， 以 甲苯 为溶剂， 反应 1.0h， 以78%的产率得到2,3,4,2',3'-penta-O-benzyl-4',6'-O-benzylidene-α,α-D-trehalose
  参考文献：
  名称：

  海藻糖Desymmetrization通过亚苄基的区域选择性还原DIBAL开环和亚苄基缩醛取代†

  摘要：

  使用在水中制备的DIBAL储备溶液，以区域选择性的方式在O6或O4处还原海藻糖二苄基和取代的二苄基缩醛。 甲苯 或者 二氯甲烷分别实现海藻糖核心的去对称化。该方法被用于合成各种生物学上重要的不对称取代的海藻糖糖结合物，包括分枝杆菌三糖，4-表位-海藻糖类似物和马拉多脂。

  DOI：

  10.1039/c3ob41389f

文献信息

• ?-D-Glycosyl-Substituted ?,?-D-Trehaloses with (1 ? 4)-Linkage: Syntheses and NMR Investigations
  作者：Hans Peter Wessel、Gerhard Englert、Peter Stangier

  DOI：10.1002/hlca.19910740403

  日期：1991.6.19

  Two symmetrical trehalose glycosyl ‘acceptors’ 4 and 6 were prepared and three of the unsymmetrical type, 8, 10, and 11. Glucosylation of symmetrical ‘acceptor’ 4 gave a higher yield of trisaccharide (44%) than protect ve-group manipulation, namely via selective debenzylidenation 2 9 or monoacetylation 2 5 which proceeded in moderate yields (33–34%). A comparison of catalysts in the cis-glucosylation

  两个对称的海藻糖的糖基“受体” 4和6中制备和三个非对称型的，8，10，和11。对称的“受体” 4的糖基化比保护ve-基团操纵（即通过选择性脱苄基2 9或单乙酰化2 5）获得的三糖收率更高（44％），中等收率（33-34％）。海藻糖“受体” 10与四-O-苄基-β-D-吡喃葡萄糖基氟13的顺式-葡萄糖基化反应中催化剂的比较异三氟甲磺酸酐（（Tf）2 O）作为新的反应性启动子，产生92％的三糖14，解封得到目标糖α-D-吡喃葡萄糖基-（1 4）-α，α-D-海藻糖。对大多数化合物的1 H-NMR光谱进行了广泛的分析。提倡使用ID TOCSY技术的时间效率，如果需要的话还可以通过ROESY实验进行补充。
• Comparison of catalysts in α-glucosylation reactions and identification of triflic anhydride as a new reactive promoter.
  作者：Hans Peter Wessel

  DOI：10.1016/s0040-4039(00)97191-0

  日期：1990.1

  Triflic anhydride is shown to be a highly reactive promoter in the cisglycosylation reaction of 2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl fluoride with an unreactive glycosyl acceptor.

  在2,3,4,6-四-O-苄基-β-D-吡喃葡萄糖基氟与不反应的糖基受体的顺式糖基化反应中，三氟甲磺酸被显示为高反应性的启动子。
• The synthesis of further analogues of trehalose containing amino and fluoro substituents
  作者：Anthony F. Hadfield、Leslie Hough、Anthony C. Richardson

  DOI：10.1016/s0008-6215(00)85320-3

  日期：——

  derivative of 4,6-diacetamido-4,6-dideoxy-α- d -glucopyranosyl α- d -glucopyranoside, via nucleophilic displacement reactions of appropriate sulphonic esters or chlorodeoxy derivatives, are described. The synthesis of the symmetrical derivative 4-amino-4,6-dideoxy-6-fluoro-α- d -galactopyranosyl 4-amino-4,6-dideoxy-6-fluoro-α- d -galactopyranoside is also described. The 19F-n.m.r. spectra of the salts of the

  摘要4,6-二乙酰氨基-4,6-二脱氧-α-d-吡喃半乳糖基，4-氨基-4,6-二脱氧-6-氟-α-d-吡喃半乳糖基和4,6-二乙酰氨基的衍生物的合成通过适当的磺酸酯或氯脱氧衍生物的亲核取代反应，描述了-4，6-二脱氧-α-d-吡喃葡萄糖基α-d-吡喃葡萄糖苷。还描述了对称衍生物4-氨基-4，6-二脱氧-6-氟代-α-d-吡喃半乳糖苷的合成4-氨基-4，6-二脱氧-6-氟-α-d-吡喃半乳糖苷。4-氨基-6-氟化物的盐的19F-nmr光谱揭示了由于6-CF和4-CN+之间的偶极引力引起的关于C-5C-6键的意外构象债券。
• Desymmetrization of trehalose via regioselective DIBAL reductive ring opening of benzylidene and substituted benzylidene acetals
  作者：Vikram A. Sarpe、Suvarn S. Kulkarni

  DOI：10.1039/c3ob41389f

  日期：——

  Trehalose dibenzylidene and substituted dibenzylidene acetals were reductively opened either at O6 or O4 in a regioselective manner by using a DIBAL stock solution prepared in toluene or dichloromethane, respectively, to achieve desymmetrization of the trehalose core. The method was applied to synthesize various biologically important unsymmetrically substituted trehalose glycoconjugates, including

  使用在水中制备的DIBAL储备溶液，以区域选择性的方式在O6或O4处还原海藻糖二苄基和取代的二苄基缩醛。 甲苯 或者 二氯甲烷分别实现海藻糖核心的去对称化。该方法被用于合成各种生物学上重要的不对称取代的海藻糖糖结合物，包括分枝杆菌三糖，4-表位-海藻糖类似物和马拉多脂。
• Selectively Deoxygenated Derivatives of β-Maltosyl-(1→4)-Trehalose as Biological Probes
  作者：Hans Peter Wessel、Michel Trumtel、Rudolf Minder

  DOI：10.1080/07328309608005672

  日期：1996.7

  The four derivatives of beta-maltosyl-(1 --> 4)-trehalose have been synthesized, which are monodeoxygenated at the site of one of the primary hydroxyl groups. The tetrasaccharides were constructed in [2+2] block syntheses. Thus, 6'''-deoxy-beta-maltosyl-(1 --> 4)-trehalose was prepared by selective iodination of allyl 2,3,6,2',3'-penta-O-acetyl-beta-maltoside (3) followed by catalytic hydrogenolysis and coupling with 2,3-di-O-benzyl-4,6-O-benzylidene-alpha-D-glucopyranosyl 2',3',6'-tri-O-benzyl-alpha-D-glucopyranoside (9), and 6 ''-deoxy-beta-maltosyl-(1 --> 4)-trehalose by selective iodination of allyl 4',6'-O-isopropylidene-beta-maltoside (14), coupling with 9, and one-step hydrogenolysis at the tetrasaccharide level. For the synthesis of 6'-deoxy-beta-maltosyl-(1 --> 4)-trehalose, the diol 2,3-di-O-benzyl-4,6-O-benzylidene-alpha-D-glucopyranosyl 2',3'-di-O-benzyl-alpha-D-glucopyranoside (22) was selectively iodinated and glycosylated with acetobromomaltose followed by catalytic hydrogenolysis. The 6-deoxy-beta-maltosyl-(1 --> 4)-trehalose was obtained upon selective iodination of a tetrasaccharide diol.