methyl (dimethylthexylsilyl 3-O-pivaloyl-β-L-idopyranosyl)uronate | 835605-28-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl (dimethylthexylsilyl 3-O-pivaloyl-β-L-idopyranosyl)uronate
• 英文别名: methyl (dimethylthexylsilyl 3-O-pivaloyl-β-L-idopyranosid)uronate；methyl (2R,3S,4S,5R,6R)-6-[2,3-dimethylbutan-2-yl(dimethyl)silyl]oxy-4-(2,2-dimethylpropanoyloxy)-3,5-dihydroxyoxane-2-carboxylate
• CAS: 835605-28-2
• 化学式: C₂₀H₃₈O₈Si
• 分子量: 434.602
• InChiKey: MWDDPGFUCQBHRN-LVNYTYFRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.22
• 重原子数：
  29
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  112
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  methyl (dimethylthexylsilyl 3-O-pivaloyl-β-L-idopyranosyl)uronate 在 scandium tris(trifluoromethanesulfonate) 2,6-二甲基吡啶 、 4-二甲氨基吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 28.0h， 生成 methyl dimethylthexylsilyl 2-O-acetyl-4-O-levulinoyl-3-O-pivaloyl-β-L-idopyranosiduronate
  参考文献：
  名称：

  选择性Sc（OTf）3催化的三烷基甲硅烷基醚与β-1-1-氨基吡喃糖苷和3,4-O-异亚丙基-β-d-吡喃半乳糖苷衍生物的乙酰酯交换反应

  摘要：

  单糖结构单元的选择性甲硅烷基化可用于制备复杂的低聚糖。我们现在报告，二醇，甲基（二甲基甲硅烷基甲硅烷基3-O-新戊酰基-β-L-氨基吡喃基）尿酸酯，可以被三烷基甲硅烷基三氟甲磺酸酯在O-2位置选择性甲硅烷基化。在保护O-4之后，通过利用在乙酸酐存在下Sc（OTf）3催化的三烷基甲硅烷基乙酸酯交换反应，可以用乙酸酯选择性地取代O-2甲硅烷基。对于三乙基甲硅烷基（TES），叔丁基二甲基甲硅烷基（TBS）和三异丙基甲硅烷基（TIPS），显示出高的O-2选择性。选择性裂解反应仅适用于TES和TBS衍生物。选择的甲硅烷基三氟甲磺酸酯和甲硅烷基氯用作与3,4-O-异亚丙基-1-硫代-硫代-β-D-吡喃半乳糖苷的甲硅烷基化试剂。大多数情况下，甲硅烷基化以高收率提供了2,6-二-O-甲硅烷基化的产物。裂解反应的研究表明，只有主要的甲硅烷基化的保护基被乙酰基取代。该反应与多种甲硅烷基保护基一起起作用，但不适

  DOI：

  10.1016/j.carres.2004.10.006
• 作为产物：
  描述：

  D-glucurono-3,6-lactone acetonide 在 吡啶 、 咪唑 、 水 、 三乙胺 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 methyl (dimethylthexylsilyl 3-O-pivaloyl-β-L-idopyranosyl)uronate
  参考文献：
  名称：

  A short route to l-iduronic acid building blocks for the syntheses of heparin-like disaccharides

  摘要：

  The effective preparation of differentially protected L-iduronic acid derivatives, as building blocks for the synthesis of heparin-like oligosaccharides, is described in less than nine steps starting from readily available 1,2-O-isopropylidene-6,3-D-glucuronolactone. The pivaloyl group was used as a permanent protecting group of hydroxyl groups. Two heparin-like disaccharides with different sulfation pattern have been prepared by using these L-iduronic acid building blocks. Crown Copyright (C) 2003 Published by Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2003.08.092

文献信息

• Development of specific inhibitors for heparin-binding proteins based on the cobra cardiotoxin structure: an effective synthetic strategy for rationally modified heparin-like disaccharides and a trisaccharide
  作者：Weijun Ke、Dennis M. Whitfield、Jean-Robert Brisson、Gary Enright、Harold C. Jarrell、Wen-guey Wu

  DOI：10.1016/j.carres.2004.11.029

  日期：2005.2

  Recently, a new heparin disaccharide-binding site on the convex side of cobra cardiotoxin (CTX) was identified by NMR spectroscopy and molecular modeling. To further characterize this site two heparin-like disaccharides were synthesized for binding studies with CTX, and a trisaccharide was synthesized for testing the sequence of the disaccharide binding to CTX. Thus six differentially protected monosaccharide building blocks (three L-iduronic acids and three D-glucosamines) were prepared. These include a L-iduronic acid elongation building block namely methyl 2-O-acetyl-4-O-levulinoyl-3-O-pivaloyl-alpha-L-idopyranosyluronate trichloroacetimidate for which a single-crystal X-ray structure was determined to have M-r = 576.79, a = 9.3098(11) Angstrom alpha = 90degrees, b = 10.3967(12) Angstrom beta = 90degrees, c = 28.026(3) Angstrom gamma = 90degrees, V = 2712.7(6) Angstrom(3), P2(1)2(1)2(1), Z = 4, mu = 0.71073 Angstrom, and R = 0.0378 for 7586 observed reflections. It shows that the molecular structure of the donor is in the C-1(4) conformation with significant 1,3-diaxial interactions between O-1 and O-3 as well as O-2 and O-4. The disaccharides and trisaccharide vary in the degree and position of O- and N-sulfation. The pivaloyl group was used as permanent protecting group of hydroxyl. The levulinoyl group was used as the temporary protecting group to protect the hydroxyl for elongation. Crown Copyright (C) 2005 Published by Elsevier Ltd. All rights reserved.
• A short route to l-iduronic acid building blocks for the syntheses of heparin-like disaccharides
  作者：Weijun Ke、Dennis M Whitfield、Manjinder Gill、Suzon Larocque、Siu-Hong Yu

  DOI：10.1016/j.tetlet.2003.08.092

  日期：2003.10

  The effective preparation of differentially protected L-iduronic acid derivatives, as building blocks for the synthesis of heparin-like oligosaccharides, is described in less than nine steps starting from readily available 1,2-O-isopropylidene-6,3-D-glucuronolactone. The pivaloyl group was used as a permanent protecting group of hydroxyl groups. Two heparin-like disaccharides with different sulfation pattern have been prepared by using these L-iduronic acid building blocks. Crown Copyright (C) 2003 Published by Elsevier Ltd. All rights reserved.
• A selective Sc(OTf)3-catalyzed trialkylsilyl ether to acetyl ester exchange reaction with β-l-idopyranoside and 3,4-O-isopropylidene-β-d-galactopyranoside derivatives
  作者：Weijun Ke、Dennis M. Whitfield

  DOI：10.1016/j.carres.2004.10.006

  日期：2004.12

  be selectively replaced by acetate by taking advantage of a trialkylsilyl-acetate exchange reaction catalyzed by Sc(OTf)3 in the presence of acetic anhydride. The high O-2 selectivity is shown for triethylsilyl (TES), tert-butyldimethylsilyl (TBS), and triisopropylsilyl (TIPS). The selective cleavage reaction only worked well for TES and TBS derivatives. A selection of silyl triflates and silyl chlorides

  单糖结构单元的选择性甲硅烷基化可用于制备复杂的低聚糖。我们现在报告，二醇，甲基（二甲基甲硅烷基甲硅烷基3-O-新戊酰基-β-L-氨基吡喃基）尿酸酯，可以被三烷基甲硅烷基三氟甲磺酸酯在O-2位置选择性甲硅烷基化。在保护O-4之后，通过利用在乙酸酐存在下Sc（OTf）3催化的三烷基甲硅烷基乙酸酯交换反应，可以用乙酸酯选择性地取代O-2甲硅烷基。对于三乙基甲硅烷基（TES），叔丁基二甲基甲硅烷基（TBS）和三异丙基甲硅烷基（TIPS），显示出高的O-2选择性。选择性裂解反应仅适用于TES和TBS衍生物。选择的甲硅烷基三氟甲磺酸酯和甲硅烷基氯用作与3,4-O-异亚丙基-1-硫代-硫代-β-D-吡喃半乳糖苷的甲硅烷基化试剂。大多数情况下，甲硅烷基化以高收率提供了2,6-二-O-甲硅烷基化的产物。裂解反应的研究表明，只有主要的甲硅烷基化的保护基被乙酰基取代。该反应与多种甲硅烷基保护基一起起作用，但不适