3-O-benzyl-5-O-(tert-butyldimethylsilyl)-1,2-O-isopropylidene-α-D-xylofuranose | 167500-61-0

• 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-benzyl-5-O-(tert-butyldimethylsilyl)-1,2-O-isopropylidene-α-D-xylofuranose
• 英文别名: [(3aR,5R,6S,6aR)-2,2-dimethyl-6-phenylmethoxy-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-5-yl]methoxy-tert-butyl-dimethylsilane
• CAS: 167500-61-0
• 化学式: C₂₁H₃₄O₅Si
• 分子量: 394.583
• InChiKey: BIPMBSVXHDQKBF-FCGDIQPGSA-N

物化性质

• 沸点：
  150-152 °C(Press: 0.002 Torr)
• 密度：
  1.07±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.47
• 重原子数：
  27
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.71
• 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：

  3-O-benzyl-5-O-(tert-butyldimethylsilyl)-1,2-O-isopropylidene-α-D-xylofuranose 在 氯化锆(IV) 作用下， 以 乙腈 为溶剂， 反应 0.75h， 以80%的产率得到3-O-benzyl-1,2-O-isopropylidene-α-D-xylofuranose
  参考文献：
  名称：

  简便的氯化锆（IV）催化叔丁基二甲基甲硅烷基（TBDMS）醚的选择性脱保护

  摘要：

  报告了一种简单有效的方案，可在20-45分钟内以高收率使用20 mol％ZrCl 4选择性脱保护叔丁基二甲基甲硅烷基（TBDMS）醚，其中证明了对酸和碱敏感的基团，烯丙基和苄基团体不受影响。

  DOI：

  10.1016/s0040-4039(03)01088-8
• 作为产物：
  描述：

  1,2:3,5-双-O-异亚丙基-alpha-D-呋喃木糖 在 咪唑 、 盐酸 、 sodium hydride 作用下， 以 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 3.5h， 生成 3-O-benzyl-5-O-(tert-butyldimethylsilyl)-1,2-O-isopropylidene-α-D-xylofuranose
  参考文献：
  名称：

  Synthesis and biological evaluation of deoxy salacinols, the role of polar substituents in the side chain on the α-glucosidase inhibitory activity

  摘要：

  Three analogs (5, 6, and 7) lacking polar substituents in the side chain of a naturally occurring a-glucosidase inhibitor, salacinol (la), were synthesized by the coupling reaction of a thiosugar, 1,4-dideoxy-1,4-epithio-D-arabinitol (3), with cyclic sulfates (8, 9, and 10), and their a-glucosidase inhibitory activities were examined. All these simpler analogs (5, 6, and 7) showed less inhibitory activity compared to la, and proved the importance of cooperative role of the polar substituents for the a-glucosidase inhibitory activity. A practical synthetic route to 3 starting from D-xylose is also described. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2005.08.040

文献信息

• A facile zirconium(IV) chloride catalysed selective deprotection of t-butyldimethylsilyl (TBDMS) ethers
  作者：G.V.M. Sharma、B. Srinivas、Palakodety Radha Krishna

  DOI：10.1016/s0040-4039(03)01088-8

  日期：2003.6

  A simple and efficient protocol for the selective deprotection of t-butyldimethylsilyl (TBDMS) ethers using 20 mol% ZrCl4 in 20–45 min and in high yields, is reported, wherein it is demonstrated that acid and base sensitive groups and allylic and benzylic groups are unaffected.

  报告了一种简单有效的方案，可在20-45分钟内以高收率使用20 mol％ZrCl 4选择性脱保护叔丁基二甲基甲硅烷基（TBDMS）醚，其中证明了对酸和碱敏感的基团，烯丙基和苄基团体不受影响。
• Total Synthesis of Cephalosporolide E via a Tandem Radical/Polar Crossover Reaction. The Use of the Radical Cations under Nonoxidative Conditions in Total Synthesis
  作者：Omar Cortezano-Arellano、Leticia Quintero、Fernando Sartillo-Piscil

  DOI：10.1021/jo502757c

  日期：2015.3.6

  The present work reports the first example of the use of the chemistry of radical cations under nonoxidative conditions in total synthesis. Using a late-stage tandem radical/polar crossover reaction, a highly stereoselective total synthesis of cephalosporolide E (which is typically obtained admixed with cephalosporolide F) was accomplished. The reaction of a phthalimido derivative with triphenyltin

  本工作报道了在全合成中在非氧化条件下使用自由基阳离子化学的第一个例子。使用后期串联自由基/极性交叉反应，完成了头孢菌素E的高度立体选择性全合成（通常与头孢菌素F混合获得）。邻苯二甲酰亚胺衍生物与三苯基锡自由基在回流的甲苯中的反应产生了一个接触离子对（自由基阳离子），该对离子对首先导致头孢内酯F，后者通过立体异构化的螺线型异构化而被转化为头孢内酯E。串联转化过程中形成的磷酸二苯酯酸。
• Bearder, John R.; Dewis, Mark L.; Whiting, Donald A., Journal of the Chemical Society. Perkin transactions I, 1995, p. 227 - 234
  作者：Bearder, John R.、Dewis, Mark L.、Whiting, Donald A.

  DOI：——

  日期：——
• Exploiting π shielding interactions of η6 arene chromium (0) complexes: New auxiliaries derived from the biogenic chiral pool
  作者：Jane Li、Longfei Xie、Mustafa Guzel、Steven B. Heaton、Dong Ma、Amy E. Kallmerten、Graham B. Jones

  DOI：10.1016/j.jorganchem.2007.09.005

  日期：2007.11

  A family of highly selective chiral auxiliaries containing arene chromium (0) complexes has been prepared using biogenic precursors from the chiral pool. The systems, derived from isomannide, prolinol, and xylofuranose were applied to the asymmetric Diels–Alder reaction of derived acrylate esters. Factors influencing stereoselectivity with the auxiliaries have been investigated and delineated including

  使用手性库中的生物前体制备了一系列含有芳烃铬（0）配合物的高选择性手性助剂。衍生自异甘露糖苷，脯氨醇和木呋喃糖的体系应用于衍生的丙烯酸酯的不对称Diels-Alder反应。已经研究并描述了影响助剂立体选择性的因素，包括混合配体对铬（0）配合物的影响。在最佳条件下，与环戊二烯进行环加成时，助剂的ee> 95％，exo：endo比率为98：2 。
• Synthesis and biological evaluation of deoxy salacinols, the role of polar substituents in the side chain on the α-glucosidase inhibitory activity
  作者：Osamu Muraoka、Kazuya Yoshikai、Hideo Takahashi、Toshie Minematsu、Guangxin Lu、Genzoh Tanabe、Tao Wang、Hisashi Matsuda、Masayuki Yoshikawa

  DOI：10.1016/j.bmc.2005.08.040

  日期：2006.1

  Three analogs (5, 6, and 7) lacking polar substituents in the side chain of a naturally occurring a-glucosidase inhibitor, salacinol (la), were synthesized by the coupling reaction of a thiosugar, 1,4-dideoxy-1,4-epithio-D-arabinitol (3), with cyclic sulfates (8, 9, and 10), and their a-glucosidase inhibitory activities were examined. All these simpler analogs (5, 6, and 7) showed less inhibitory activity compared to la, and proved the importance of cooperative role of the polar substituents for the a-glucosidase inhibitory activity. A practical synthetic route to 3 starting from D-xylose is also described. (c) 2005 Elsevier Ltd. All rights reserved.