2,6-Anhydro-3,4,5,7-tetra-O-benzyl-aldehydo-D-glycero-D-ido-heptopyranose | 113019-43-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,6-Anhydro-3,4,5,7-tetra-O-benzyl-aldehydo-D-glycero-D-ido-heptopyranose
• 英文别名: (2,3,4,6-O-tetrabenzyl-α-D-glucopyranosyl)carboxaldehyde；2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl formaldehyde；(2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl)methanal；(2S,3R,4S,5R,6R)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxane-2-carbaldehyde
• CAS: 113019-43-5
• 化学式: C₃₅H₃₆O₆
• 分子量: 552.667
• InChiKey: KKPOREZWWWRARY-CKQPALCZSA-N

物化性质

• 沸点：
  673.6±55.0 °C(Predicted)
• 密度：
  1.20±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  41
• 可旋转键数：
  14
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2,6-Anhydro-3,4,5,7-tetra-O-benzyl-aldehydo-D-glycero-D-ido-heptopyranose 在 溴 、 sodium acetate 作用下， 以 甲醇 、 水 为溶剂， 生成 (2S,3R,4S,5R,6R)-3,4,5-Tris-benzyloxy-6-benzyloxymethyl-tetrahydro-pyran-2-carboxylic acid methylamide
  参考文献：
  名称：

  X-Ray crystallographic analysis of 2,6-anhydro-N-methyl-D-glycero-D-ido-heptonamide: the first example of a simple glucose analogue with a skew boat structure

  摘要：

  对2,6-脱水-N-甲基-D-甘油-D-异庚酰胺的单晶X射线晶体学分析和与糖原磷酸酶的晶体结合研究表明，葡萄糖类似物具有意想不到的歪斜船形构象。

  DOI：

  10.1039/c39930000654
• 作为产物：
  描述：

  2,3,4,6-四苄基-D-吡喃葡萄糖 在 三乙基硅烷 、 正丁基锂 、 三氟甲磺酸三甲基硅酯 、 4 A molecular sieve 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 反应 2.33h， 生成 2,6-Anhydro-3,4,5,7-tetra-O-benzyl-aldehydo-D-glycero-D-ido-heptopyranose
  参考文献：
  名称：

  Thiazole-Based Synthesis of Formyl C-Glycosides

  摘要：

  A method for the installation of the formyl group at the anomeric position of pyranoses and furanoses starting from the corresponding lactones has been developed. The strategy involves the addition of 2-lithiothiazole to the sugar lactone, followed by the silane reduction of the acetylated resultant ketol and the unmasking of the formyl group from the thiazole ring. All steps have been studied in some details to improve chemical efficiency and stereochemical control. Hence, reversed alpha:beta ratios of ketols were found in kinetic and thermodynamic mixtures, the former being consistent with a steric effect control of the substituents and the latter by the electronic effect of the ring oxygen. Seven sugar aldehydes with different D-pyranosidic (2,3,4,6-tetra-O-benzyl-gluco, -galacto, and -manno, 2-azido-3,4,6-tri-O-benzyl-2-deoxy-galacto) and D-furanosidic moieties (5-O-benzyl-2,3-isopropylidene-ribo; 2,3,5-tri-O-benzyl-ribo; 2,3:5,6-di-O-isopropylidene-manno) were prepared in 52-65% isolated overall yield from the corresponding lactone.

  DOI：

  10.1021/jo00100a050

文献信息

• Multigram scale synthesis of formyl tetra-O-benzyl-β-d-C-glucopyranoside using benzothiazole as a formyl group equivalent
  作者：Alessandro Dondoni、Alberto Marra

  DOI：10.1016/s0040-4039(02)02525-x

  日期：2003.1

  β-d-glucopyranoside; treatment of this mixture with sodium methoxide gives the β-anomer from which the title aldehyde is obtained in a pure form by transformation of the benzothiazole ring into the formyl group.

  向d-葡糖酸内酯中加入2-硫代苯并噻唑，然后将所得酮糖脱氧，得到苯并噻唑基α-和β-d-吡喃葡萄糖苷的混合物。用甲醇钠处理该混合物得到β-异头物，通过将苯并噻唑环转化成甲酰基，以纯净形式得到标题醛。
• An efficient method for the synthesis of α- and β-c-glycosyl aldehydes
  作者：William R. Kobertz、Carolyn R. Bertozzi、Mark D. Bednarski

  DOI：10.1016/s0040-4039(00)77703-3

  日期：1992.2

  A practical method for the synthesis of α- and β-C-glycosyl aldehydes from a single carbohydrate precursor is described.

  描述了从单一碳水化合物前体合成α-和β- C-糖基醛的实用方法。
• Preparation of 1-C-glycosyl aldehydes by reductive hydrolysis
  作者：Szabolcs Sipos、István Jablonkai

  DOI：10.1016/j.carres.2011.04.019

  日期：2011.9

  carried out using DIBAL-H to form aldimine alane intermediates which were then hydrolyzed under mildly acidic condition to provide the corresponding aldehyde derivatives. While 1-C-formyl glycal and 2-deoxy glycosyl derivatives were stable during isolation and storage 1-C-glycosyl formaldehydes in the gluco, galacto and manno series were sensitive and decomposition occurred by 2-alkyloxy elimination

  使用DIBAL-H进行各种保护的糖基氰化物的还原水解以形成醛亚胺铝烷中间体，然后将其在中等酸性条件下水解以提供相应的醛衍生物。尽管1-C-甲酰基糖基和2-脱氧糖基衍生物在分离和存储过程中是稳定的，但葡萄糖，半乳糖和甘露糖系列中的1-C-糖基甲醛很敏感，并且通过2-烷氧基消除发生了分解。开发了一种使用N，N'-二苯基乙二胺以稳定形式捕集这些醛的一锅法。糖基氰化物的还原水解以方便的方式提供了有价值的醛结构单元，可用于合成复杂的C-糖苷。
• Preparation of 2-amino-2-C-glycosyl-acetonitriles from C-glycosyl aldehydes by Strecker reaction
  作者：Szabolcs Sipos、István Jablonkai、Orsolya Egyed、Mátyás Czugler

  DOI：10.1016/j.carres.2011.10.023

  日期：2011.12

  Synthesis of new 2-amino-2-C-D-glycosyl-acetonitriles in a Strecker reaction from various C-glycosyl aldehydes, chiral amines, and HCN was carried out. While aminonitriles from glycal and 2-deoxy-beta-D-glycosyl aldehydes were prepared in satisfactory yields, lower yields were obtained with C-glycosyl aldehydes. Strecker reaction with the benzyl-protected 1-C-formyl-D-galactal and S- or R-1-phenylethylamine (S-PEA or R-PEA) yielded predominantly the R-configured C-glycosyl aminoacetonitrile. The direction of the nucleophilic addition appears to be governed by the configuration of the anomeric carbon with beta-linked sugars. Since the stereochemistry of the transition state is unknown according to the configuration of the major product a Felkin-Ahn selectivity can be mainly presumed. (C) 2011 Elsevier Ltd. All rights reserved.
• Thiazole-based synthesis of C-glycosyl aldehydes
  作者：Alessandro Dondoni、Marie-Christine Scherrmann

  DOI：10.1016/s0040-4039(00)79319-1

  日期：1993.11

  The formylation at the anomeric carbon of the model sugars 2,3,4,6-tetra-O-benzyl-D-glucopyranose and 2,3:5,6-di-O-isopropylidene-D-mannofuranose is carried out by addition of 2-lithiothiazole to the corresponding lactones followed by reductive dehydroxylation and thiazole to formyl deblocking.