dimethyl [(3R,4S,5R,6R)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-yl] phosphite | 208466-14-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: dimethyl [(3R,4S,5R,6R)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-yl] phosphite
• CAS: 208466-14-2
• 化学式: C₃₆H₄₁O₈P
• 分子量: 632.69
• InChiKey: NKFCEJUKCPDRQP-KXCACMGXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  45
• 可旋转键数：
  17
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  73.8
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  dimethyl [(3R,4S,5R,6R)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-yl] phosphite 在 palladium dihydroxide 吡啶 、 咪唑 、 2,6-二甲基吡啶 、 4-二甲氨基吡啶 、 4 A molecular sieve 、 氢氟酸 、 氢气 、 碘 、 silver perchlorate 、 三乙胺 、 三苯基膦 、 zinc(II) chloride 作用下， 以 甲醇 、 二氯甲烷 、 乙腈 、 苯 为溶剂， 25.0 ℃ 、101.33 kPa 条件下， 反应 93.17h， 生成
  参考文献：
  名称：

  Total synthesis of (.+-.)-paeoniflorigenin and paeoniflorin

  摘要：

  DOI：

  10.1021/ja00072a063
• 作为产物：
  描述：

  2,3,4,6-四苄基-D-吡喃葡萄糖 、 N,N-二异丙基亚膦酸二甲酯酰胺 在 四氮唑 作用下， 以 二氯甲烷 为溶剂， 反应 1.28h， 生成 dimethyl [(3R,4S,5R,6R)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-yl] phosphite
  参考文献：
  名称：

  Glycosylation of alcohols using glycosyl boranophosphates as glycosyl donors

  摘要：

  A novel glycosylation that uses glycosyl boranophosphate triesters as glycosyl donors and trityl cation (Tr+) as an activator was developed. Two types of reactions were studied: (1) the boranophosphate triester was activated with TrNTf2 to react with an alcohol and (2) O-trityl ethers worked as both glycosyl acceptors and Tr+ sources. The latter gave better results and the desired O-glycosylation products were rapidly generated and isolated in moderate to good yields. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2013.04.032

文献信息

• Activation of Glycosyl Phosphites under Neutral Conditions in Solutions of Metal Perchlorates in Organic Solvents
  作者：Heidrun Schene、Herbert Waldmann

  DOI：10.1002/(sici)1099-0690(199806)1998:6<1227::aid-ejoc1227>3.0.co;2-4

  日期：1998.6

  Glycosyl phosphites 1–3 derived from glucose are activated under neutral conditions and without the addition of any further promoter in 1 M solutions of LiClO4, Mg(ClO4)2 or Ba(ClO4)2 in ether, CH2Cl2, or CH3CN and react under these conditions with the alcohols5–9 to give the glycosides 10–14. The best results are obtained in the presence of Ba(ClO4)2. In CH2Cl2 and ether the α-anomers predominate

  源自葡萄糖的糖基亚磷酸酯 1-3 在中性条件下被活化，并且在 Li 、Mg(ClO4)2 或 Ba( )2 在乙醚、CH2Cl2 或 CH3CN 中的 1 M 溶液中无需添加任何其他促进剂，并在这些条件下反应条件与醇5-9 得到糖苷10-14。在 Ba( )2 存在下获得最佳结果。在 和醚中，α-异构体占主导地位，在 CH3CN 中，β-异构体过量形成。亚磷酸甲酯 1 和亚磷酸苄酯 3 以 35-66% 的产率提供所需的糖苷，而亚磷酸乙酯 2 是更具反应性的糖基供体，以 62-95% 的产率产生糖苷 10、11 和 13。
• Glycosylation using glycosyl phosphite as a glycosyl donor
  作者：Yutaka Watanabe、Chikara Nakamoto、Takashi Yamamoto、Shoichiro Ozaki

  DOI：10.1016/s0040-4020(01)89683-6

  日期：——

  Glycosylation using glycosyl phosphites as glycosyl donors in the presence of a Lewis acid such as ZnCl2 or ZnCl2-AgClO4 has afforded the glycosides including sialoglycosides in good yields.
• Stereoselective Synthesis of α-Glycosyl Phosphites and Phosphoramidites via <i>O</i>-Selective Glycosylation of <i>H</i>-Phosphonate Derivatives
  作者：Fumiko Matsumura、Natsuhisa Oka、Takeshi Wada

  DOI：10.1021/ol802190x

  日期：2008.11.20

  A highly stereo- and chemoselective glycosylation of H-phosphonate derivatives with glycosyl iodides was discovered as a reverse reaction of the formation of a glycosyl iodide from a glycosyl phosphite and I- under mild acidic conditions. Further study on the unique reaction showed that the reaction provided various alpha-glycosyl phosphites; and phosphoramidites in a highly stereoselective manner with complete O-selectivity.