3-O-(tert-butyldimethylsilyl)oxy-4-O-benzyl-L-rhamnal | 293736-30-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3-O-(tert-butyldimethylsilyl)oxy-4-O-benzyl-L-rhamnal
• 英文别名: tert-butyl-dimethyl-[[(2S,3S,4S)-2-methyl-3-phenylmethoxy-3,4-dihydro-2H-pyran-4-yl]oxy]silane
• CAS: 293736-30-8
• 化学式: C₁₉H₃₀O₃Si
• 分子量: 334.531
• InChiKey: IKNLWHGBJJTBBF-SZMVWBNQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.89
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-O-(tert-butyldimethylsilyl)oxy-4-O-benzyl-L-rhamnal 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 20.0h， 以12.76 g的产率得到4-O-苄基-L-鼠李醛
  参考文献：
  名称：

  Kijanimicin 的 α-连接的洋地黄毒苷三糖片段的合成：糖基磺酸盐的意外应用

  摘要：

  以前，我们证明了糖基甲苯磺酸盐可有效合成葡萄糖配置的 2-脱氧糖的 β-糖苷。在这里，我们展示了相同的磺酸盐系统可用于选择性合成含有同种异体配置的 2-脱氧糖地黄糖的 α-糖苷。与以前的工作一样，通过将供体与适当的芳基磺酰氯促进剂匹配来获得最佳选择性。通过合成 kijanimicin 的 α-连接的洋地黄毒三糖片段证明了该方法的实用性。

  DOI：

  10.1021/acs.orglett.1c04190
• 作为产物：
  描述：

  2,3,4-tri-O-acetyl-L-rhamnopyranosyl bromide 在 甲醇 、 4-二甲氨基吡啶 、 sodium methylate 、 sodium hexamethyldisilazane 、 三乙胺 、 锌 作用下， 以 四氢呋喃 、 aq. phosphate buffer 、 乙酸乙酯 、 N,N-二甲基甲酰胺 为溶剂， 反应 0.82h， 生成 3-O-(tert-butyldimethylsilyl)oxy-4-O-benzyl-L-rhamnal
  参考文献：
  名称：

  Automated, Multistep Continuous‐Flow Synthesis of 2,6‐Dideoxy and 3‐Amino‐2,3,6‐trideoxy Monosaccharide Building Blocks

  摘要：

  AbstractAn automated continuous flow system capable of producing protected deoxy‐sugar donors from commercial material is described. Four 2,6‐dideoxy and two 3‐amino‐2,3,6‐trideoxy sugars with orthogonal protecting groups were synthesized in 11–32 % overall yields in 74–131.5 minutes of total reaction time. Several of the reactions were able to be concatenated into a continuous process, avoiding the need for chromatographic purification of intermediates. The modular nature of the experimental setup allowed for reaction streams to be split into different lines for the parallel synthesis of multiple donors. Further, the continuous flow processes were fully automated and described through the design of an open‐source Python‐controlled automation platform.

  DOI：

  10.1002/anie.202109887

文献信息

• Modular continuous flow synthesis of orthogonally protected 6-deoxy glucose glycals
  作者：Subbarao Yalamanchili、Tu-Anh V. Nguyen、Nicola L. B. Pohl、Clay S. Bennett

  DOI：10.1039/d0ob00522c

  日期：——

  An efficient, modular continuous flow process towards accessing two orthogonally protected glycals is described with the development of reaction conditions for several common protecting group additions in flow, including the addition of benzyl, naphthylmethyl and tert-butyldimethylsilyl ethers. The process affords the desired target compounds in 57-74% overall yield in just 21-37 minutes of flow time

  描述了一种有效的，模块化的连续流动方法，该方法旨在获得两个正交保护的糖，并为几种常见的保护基的流动反应条件的发展做出了贡献，其中包括苄基，萘基甲基和叔丁基二甲基甲硅烷基醚的添加。该方法仅在21-37分钟的流动时间内即可以57-74％的总收率提供所需的目标化合物。此外，与分批条件不同，该流动过程避免了需要主动冷却以防止有害的放热的需要，并且需要更短的反应时间。
• 4-O-Acetyl-3-O-tert-butyldimethylsilyl-l-rhamnal: a building block in the stereoselective synthesis of 2-deoxy-α-l-rhamnopyranosides
  作者：Ilona Wandzik、Tadeusz Bieg

  DOI：10.1016/j.carres.2006.09.007

  日期：2006.11

  The stereoselective synthesis of 2-deoxy-alpha-L-glycosides by addition of various acceptors to 4-O-acetyl-3-O-tert-butyldimethylsilyi-L-rhamnal promoted by triphenylphosphine-hydrogen bromide is developed. (c) 2006 Elsevier Ltd. All rights reserved.
• Direct Synthesis of 2-Deoxy-β-Glycosides via Anomeric <i>O</i>-Alkylation with Secondary Electrophiles
  作者：Danyang Zhu、Kedar N. Baryal、Surya Adhikari、Jianglong Zhu

  DOI：10.1021/ja4116956

  日期：2014.2.26

  An approach for direct synthesis of biologically significant 2-deoxy-beta-glycosides has been developed via O-alkylation of a variety of 2-deoxy-sugar-derived anomeric alkoxides using challenging secondary triflates as electrophiles. It was found a free hydroxyl group at C3 of the 2-deoxy-sugar-derived lactols is required in order to achieve synthetically efficient yields. This method has also been applied to the convergent synthesis of a 2-deoxy-beta-tetrasaccharide.
• Automated, Multistep Continuous‐Flow Synthesis of 2,6‐Dideoxy and 3‐Amino‐2,3,6‐trideoxy Monosaccharide Building Blocks
  作者：Subbarao Yalamanchili、Tu‐Anh Nguyen、Alexander Zsikla、Gavin Stamper、Ashley E. DeYong、John Florek、Olivea Vasquez、Nicola L. B. Pohl、Clay S. Bennett

  DOI：10.1002/anie.202109887

  日期：2021.10.18

  AbstractAn automated continuous flow system capable of producing protected deoxy‐sugar donors from commercial material is described. Four 2,6‐dideoxy and two 3‐amino‐2,3,6‐trideoxy sugars with orthogonal protecting groups were synthesized in 11–32 % overall yields in 74–131.5 minutes of total reaction time. Several of the reactions were able to be concatenated into a continuous process, avoiding the need for chromatographic purification of intermediates. The modular nature of the experimental setup allowed for reaction streams to be split into different lines for the parallel synthesis of multiple donors. Further, the continuous flow processes were fully automated and described through the design of an open‐source Python‐controlled automation platform.
• Synthesis of the α-Linked Digitoxose Trisaccharide Fragment of Kijanimicin: An Unexpected Application of Glycosyl Sulfonates
  作者：J. Colin Mizia、Mohammed U. Syed、Clay S. Bennett

  DOI：10.1021/acs.orglett.1c04190

  日期：2022.1.21

  gluco-configured 2-deoxy sugars. Here, we show the same sulfonate system can be used for the selective synthesis of α-glycosides containing the allo-configured 2-deoxy sugar digitoxose. As with previous work, optimal selectivity is obtained through matching the donor with the appropriate arylsulfonyl chloride promoter. The utility of this method is demonstrated through the synthesis of the α-linked digitoxose trisaccharide

  以前，我们证明了糖基甲苯磺酸盐可有效合成葡萄糖配置的 2-脱氧糖的 β-糖苷。在这里，我们展示了相同的磺酸盐系统可用于选择性合成含有同种异体配置的 2-脱氧糖地黄糖的 α-糖苷。与以前的工作一样，通过将供体与适当的芳基磺酰氯促进剂匹配来获得最佳选择性。通过合成 kijanimicin 的 α-连接的洋地黄毒三糖片段证明了该方法的实用性。