methyl 2,3,4-tri-O-benzyl-6-deoxy-6-C-formyl-α-D-mannopyranoside | 40653-17-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,3,4-tri-O-benzyl-6-deoxy-6-C-formyl-α-D-mannopyranoside
• 英文别名: 2-[(2R,3R,4S,5S,6S)-6-methoxy-3,4,5-tris(phenylmethoxy)oxan-2-yl]acetaldehyde
• CAS: 40653-17-6
• 化学式: C₂₉H₃₂O₆
• 分子量: 476.569
• InChiKey: YTXMMTWKVSJBCI-PNHLWVRCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  35
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.34
• 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：

  methyl 2,3,4-tri-O-benzyl-6-deoxy-6-C-formyl-α-D-mannopyranoside 在 samarium diiodide 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 3.25h， 生成 Dithiocarbonic acid S-methyl ester O-[1-((2S,3R,4S,5R,6R)-3,4,5-tris-benzyloxy-6-benzyloxymethyl-tetrahydro-pyran-2-yl)-2-((2R,3R,4S,5S,6S)-3,4,5-tris-benzyloxy-6-methoxy-tetrahydro-pyran-2-yl)-ethyl] ester
  参考文献：
  名称：

  Synthesis of 1,2-trans C-glycosyl compounds by reductive samariation of glycosyl iodides

  摘要：

  在羰基化合物存在的情况下，过-O-三甲基硅基或苄基吡喃糖基碘化物进行还原反应，能以良好的收率得到相应的 1,2-反式-C-糖基化合物。

  DOI：

  10.1039/b006455f
• 作为产物：
  描述：

  甲基-D-丙噻 在 咪唑 、 2,6-二甲基吡啶 、 喹啉 、 Lindlar's catalyst 、 palladium on calcium fluoride poisoned with lead 、 四丁基氟化铵 、 氢气 、 sodium hydride 、 臭氧 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 乙酸乙酯 、 N,N-二甲基甲酰胺 为溶剂， 反应 7.08h， 生成 methyl 2,3,4-tri-O-benzyl-6-deoxy-6-C-formyl-α-D-mannopyranoside
  参考文献：
  名称：

  Application of the Anomeric Samarium Route for the Convergent Synthesis of the C-Linked Trisaccharide α-d-Man-(1→3)-[α-d-Man-(1→6)]-d-Man and the Disaccharides α-d-Man-(1→3)-d-Man and α-d-Man-(1→6)-d-Man

  摘要：

  Studies are reported on the assembly of the branched C-trisaccharide, alpha-D-Man-(1-->3)-[alpha-D-Man-(1-->6)]-D-Man, representing the core region of the asparagine-linked oligosaccharides. The key step in this synthesis uses a SmI2-mediated coupling of two mannosylpyridyl sulfones to a C3,C6-diformyl branched monosaccharide unit, thereby assembling all three sugar units in one reaction and with complete stereocontrol at the two anomeric carbon centers. Subsequent tin hydride-based deoxygenation followed by a deprotection step produces the target C-trimer. In contrast to many of the other C-glycosylation methods, this approach employes intact carbohydrate units as C-glycosyl donors and acceptors, which in many instances parallels the well-studied O-glycosylation reactions. The synthesis of the C-disaccharides alpha-D-Man-(1-->3)-D-Man and alpha-D-Man-(1-->6)-D-Man is also described, they being necessary for the following conformational studies of all three carbohydrate analogues both in solution and bound to several mannose-binding proteins.

  DOI：

  10.1021/jo020339z

文献信息

• Stereoselective Synthesis of the C27–C48 Moiety of Aflastatin A by a Carbohydrate Strategy Using a Tin(II)-Mediated Aldol Reaction
  作者：Seijiro Hosokawa、Sawato Murakoshi

  DOI：10.1055/s-0035-1560572

  日期：——

  aflastatin A was synthesized by using d -mannoside and l -erythrulose derivatives as chiral building blocks. The aldol reaction of undecan-2-one with mannolactone and a subsequent reduction gave the C37 and C39 stereogenic centers with high selectivity. Another aldol reaction of a tin(II) enolate of a protected erythrulose (C27–C30 segment) with a C31–C48 aldehyde segment gave the C30,C31-syn adduct

  aflastatin A 的 C27-C48 片段是通过使用 d-甘露糖苷和 l-赤藓酮糖衍生物作为手性结构单元合成的。undecan-2-one 与甘露醇内酯的羟醛反应和随后的还原得到了具有高选择性的 C37 和 C39 立体中心。受保护的赤藓酮糖（C27-C30 链段）的锡 (II) 烯醇化物与 C31-C48 醛链段的另一个羟醛反应产生具有所需立体化学的 C30,C31-syn 加合物。组装产品的脱保护顺利进行，得到含有连续多元醇部分的 aflastatin A 的 C27-C48 片段。
• General Homologation Strategy for Synthesis of <scp>l</scp>-<i>glycero</i>- and <scp>d</scp>-<i>glycero</i>-Heptopyranoses
  作者：Shaheen K. Mulani、Kuang-Chun Cheng、Kwok-Kong T. Mong

  DOI：10.1021/acs.orglett.5b02620

  日期：2015.11.20

  A general and stereospecific homologation strategy for the synthesis of heptopyranosides is reported. The strategy employs the Wittig olefination and proline-catalyzed a-aminoxylation to achieve one carbon elongation and stereoselective hydroxylation at the C6 position, respectively. The l-glycero- and d-glycero-heptopyranosides can be obtained with nearly perfect stereoselectivity. Further study reveals the difference in the chemical shift of the C6 proton of l/d-glycero-heptopyranosyl diastereomers, which is found to be useful for assignment of the configuration of heptopyranosides.
• Anomeric Acetates ofN-Acetylneuraminic Acid are UsefulC-Sialyl Donors in Samarium-Mediated Reformatsky Coupling Reactions
  作者：Adeline Malapelle、Zouleika Abdallah、Gilles Doisneau、Jean-Marie Beau

  DOI：10.1002/anie.200601209

  日期：2006.9.11
• Miquel, Nicolas; Doisneau, Gilles; Beau, Jean-Marie, Angewandte Chemie - International Edition, 2000, vol. 39, # 22, p. 4111 - 4114
  作者：Miquel, Nicolas、Doisneau, Gilles、Beau, Jean-Marie

  DOI：——

  日期：——
• A Flexible Route to Mannose 6-Phosphonate Functionalized Derivatives
  作者：Sébastien Vidal、Jean-Louis Montero、Alain Leydet、Alain Morère

  DOI：10.1080/10426500214297

  日期：2002.10

  A new approach for the synthesis of a mannose 6-phosphonate isosteric analog of mannose 6-phosphate is reported. The mannosylphosphonate has been prepared in a multistep synthesis involving an homologation reaction of the methyl alpha-D-mannopyranoside followed by an Arbuzov reaction between a bromohomomannosyl derivative and the tris(trimethylsilyl)phosphite. This approach, avoiding the deprotection of dialkylphosphonate, allowed us to prepare the mannose 6-phosphonate in good yield. The described method was successfully extended to the preparation of a mannose 6-phosphonate linked to a cholesteryl moiety. This strategy affords a more general route for a wide range of functionalized mannose 6-phosphonate derivatives.