methyl 2,3,4-tri-O-benzyl-6,7-dideoxy-α-D-galacto-hept-6-enopyranoside | 134651-18-6

• 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-6,7-dideoxy-α-D-galacto-hept-6-enopyranoside
• 英文别名: (2R,3S,4S,5R,6S)-2-ethenyl-6-methoxy-3,4,5-tris(phenylmethoxy)oxane
• CAS: 134651-18-6
• 化学式: C₂₉H₃₂O₅
• 分子量: 460.57
• InChiKey: MLGOQFCVHKAMQL-LLQHYSMESA-N

物化性质

• 沸点：
  559.7±50.0 °C(Predicted)
• 密度：
  1.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  34
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  46.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 2,3,4-tri-O-benzyl-6,7-dideoxy-α-D-galacto-hept-6-enopyranoside 在 Raney-Ni-W₄ 吡啶 、 咪唑 、 sodium hypochlorite 、 盐酸肼 、 dimethyl sulfide borane 、 硫酸 、 氢气 、 sodium methylate 、 乙酸酐 、 溶剂黄146 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 水 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 100.0 ℃ 、101.33 kPa 条件下， 反应 12.83h， 生成 1D-4,5,6-tri-O-benzyl-2-deoxy-2-<<(1-methylethyl)diethylsilyl>oxy>methyl-chiro-inositol
  参考文献：
  名称：

  Total syntheses of glucosidase inhibitors, cyclophellitols

  摘要：

  A beta-D-glucosidase inhibitor, cyclophellitol [(1S,2R,3S,4R,5R,6R)-5-hydroxymethyl-7-oxabicyclo[4.1.0]heptane-2,3,4-triol, 1] and its epoxide diastereomer, 1,6-epicyclophellitol (2) have been synthesized by using an intramolecular [3 + 2]-cycloaddition of a nitrile oxide to an alkene as a key step. 2.3,4-Tri-O-benzyl-6,7-dideoxy-D-ido-hept-6-enose (E,Z)-oxime (6) was prepared from L-glucose in 11 steps. Intramolecular cycloaddition of 6 was realized by NaOCl via an intermediary nitrile oxide to afford the isoxazoline, (1S,2R,3S,4S,5R)-3,4,5-tribenzyloxy-2-hydroxy-8-oxa-7-azabicyclo[4.3.0]non-6-enc (7). Hydrogenolysis of 7 followed by a 5-step sequence gave cyclophellitol (1). Compound 2 was synthesized from methyl alpha-D-galactopyranoside by using a conceptually similar route. The glycosidase-inhibiting activities of 2 were examined.

  DOI：

  10.1016/0008-6215(91)89017-a
• 作为产物：
  描述：

  methyl 2,3,4-tri-O-benzyl-α-D-galactopyranoside 在 草酰氯 、 二甲基亚砜 、 三乙胺 作用下， 以 苯 为溶剂， 反应 0.67h， 生成 methyl 2,3,4-tri-O-benzyl-6,7-dideoxy-α-D-galacto-hept-6-enopyranoside
  参考文献：
  名称：

  Total syntheses of glucosidase inhibitors, cyclophellitols

  摘要：

  A beta-D-glucosidase inhibitor, cyclophellitol [(1S,2R,3S,4R,5R,6R)-5-hydroxymethyl-7-oxabicyclo[4.1.0]heptane-2,3,4-triol, 1] and its epoxide diastereomer, 1,6-epicyclophellitol (2) have been synthesized by using an intramolecular [3 + 2]-cycloaddition of a nitrile oxide to an alkene as a key step. 2.3,4-Tri-O-benzyl-6,7-dideoxy-D-ido-hept-6-enose (E,Z)-oxime (6) was prepared from L-glucose in 11 steps. Intramolecular cycloaddition of 6 was realized by NaOCl via an intermediary nitrile oxide to afford the isoxazoline, (1S,2R,3S,4S,5R)-3,4,5-tribenzyloxy-2-hydroxy-8-oxa-7-azabicyclo[4.3.0]non-6-enc (7). Hydrogenolysis of 7 followed by a 5-step sequence gave cyclophellitol (1). Compound 2 was synthesized from methyl alpha-D-galactopyranoside by using a conceptually similar route. The glycosidase-inhibiting activities of 2 were examined.

  DOI：

  10.1016/0008-6215(91)89017-a

文献信息

• Synthesis of (6,6′)-C-Linked Pseudodisaccharides
  作者：Chinmoy Mukherjee、Anup Kumar Misra

  DOI：10.1080/07328300903267577

  日期：2009.11.25

  A series of (6,6')-C-linked pseudodisaccharides has been prepared using a general synthetic strategy of olefin metathesis in the presence of Grubbs second-generation catalyst. Yields were excellent in every case.
• RCAI-61, the 6′-O-methylated analog of KRN7000: its synthesis and potent bioactivity for mouse lymphocytes to produce interferon-γ in vivo
  作者：Takuya Tashiro、Ryusuke Nakagawa、Sayo Inoue、Masao Shiozaki、Hiroshi Watarai、Masaru Taniguchi、Kenji Mori

  DOI：10.1016/j.tetlet.2008.09.074

  日期：2008.11

  RCAI-61, the 6'-O-methylated analog of KRN7000, and six other analogs with modified 6'-position of the galactose moiety of KRN7000 were synthesized to examine their bioactivity for mouse lymphocytes. Methyl alpha-D-galactopyranoside was the starting material for RCAI-58, 61, 64, 83, 85, and 86, while RCAI-87 was prepared from methyl beta-L-arabinopyranoside. Bioassay showed RCAI-61 to be a Much more potent stimulant of mouse lymphocytes than KRN7000 and RCAI-56 to induce the production of a large amount of IFN-gamma in vivo. (C) 2008 Elsevier Ltd. All rights reserved.
• RCAI-61 and related 6′-modified analogs of KRN7000: Their synthesis and bioactivity for mouse lymphocytes to produce interferon-γ in vivo
  作者：Takuya Tashiro、Ryusuke Nakagawa、Tomokuni Shigeura、Hiroshi Watarai、Masaru Taniguchi、Kenji Mori

  DOI：10.1016/j.bmc.2013.03.028

  日期：2013.6

  We synthesized ten new analogs of 6'-modified KRN7000 (A): RCAI-58, 61, 64, 83, 85-87, 113, 119, and 125. They could be synthesized by alpha-selective galactosylation of ceramide 9 with the 6-modified D-galactopyranosyl fluorides (8a-8f) or L-arabinopyranosyl fluoride (17), or by etherification of the known alcohol 19. Bioassay of the ten analogs demonstrated that RCAI-61 (1, 6'-O-methylated analog of A) was the most potent immunostimulant among them, and could induce the production of a large amount of IFN-gamma even at a low concentration in mice in vivo. (C) 2013 Elsevier Ltd. All rights reserved.
• NOVEL GLYCOLIPID AND USE THEREOF
  申请人：Riken

  公开号：EP2272854B1

  公开（公告）日：2015-08-05
• Total synthesis of gabosines via an iron-catalyzed intramolecular tandem aldol process
  作者：Dinh Hung Mac、Ramesh Samineni、Abdul Sattar、Srivari Chandrasekhar、Jhillu Singh Yadav、René Grée

  DOI：10.1016/j.tet.2011.09.121

  日期：2011.12

  Several gabosines, belonging to polyhydroxy-cyclohexenone and cyclohexanone class of natural products, are synthesized in various stereoforms using an intramolecular iron-catalyzed tandem aldol process. The reaction, which starts from vinylic pyranoses, is compatible with two different OH protecting groups (acetyl and benzyl). Further, like the Ferrier carbocyclisation, it is not sensitive to the stereochemistry of sugar molecules used as precursors: six different gabosine-type molecules have been prepared by this route starting from D-Glucose, D-Mannose, and D-Galactose derivatives. (C) 2011 Elsevier Ltd. All rights reserved.