trimethylsilyl 6-acetyl-2,3,4-tris-trimethylsilyl-α-D-glucopyranoside | 1242551-17-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: trimethylsilyl 6-acetyl-2,3,4-tris-trimethylsilyl-α-D-glucopyranoside
• 英文别名: trimethylsilyl 6-O-acetyl-2,3,4-tris-O-trimethylsilyl-α-D-glucopyranoside；[(2R,3R,4S,5R,6R)-3,4,5,6-tetrakis(trimethylsilyloxy)oxan-2-yl]methyl acetate
• CAS: 1242551-17-2
• 化学式: C₂₀H₄₆O₇Si₄
• 分子量: 510.923
• InChiKey: QNVIUFBMYOFYMS-OUUBHVDSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.79
• 重原子数：
  31
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  72.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  1,2,3,4,6-penta-O-trimethylsilyl-α-D-glucopyranose 、 乙酸酐 在 吡啶 、 溶剂黄146 作用下， 反应 48.0h， 以66%的产率得到trimethylsilyl 6-acetyl-2,3,4-tris-trimethylsilyl-α-D-glucopyranoside
  参考文献：
  名称：

  Selective Acetylation of per-O-TMS-Protected Monosaccharides

  摘要：

  Selective acetylation of various per-O-TMS-protected carbohydrates has been accomplished. Using a protecting group exchange strategy and microwave assistance, monosaccharides (glucose, galactose, and mannose) can be selectively acetylated producing either the 6-O-monoacetate or 1,6-O-diacetylated species. This new class of molecules can be deprotected without migration of the acetyl groups, providing useful synthetic intermediates. To demonstrate the scope of the reaction, the methodology was successfully extended to TMS-protected ceramide.

  DOI：

  10.1021/ol101751d

文献信息

• Development of a Karplus equation for 3JCOCH in ester-functionalized glucopyranoses and methylglucuronate.
  作者：Sven Hackbusch、Amelia Watson、Andreas H. Franz

  DOI：10.24820/ark.5550190.p010.113

  日期：——

  Empirical Karplus equations are very useful in the conformational analysis of flexible molecules, especially with regards to carbohydrates. The C(sp2)OCH dihedral angle of ester-functionalized carbohydrates, however, is not well described by widely used Karplus equations for COCH dihedral angles, because they are based on C(sp3)OCH data. Herein, we propose a three parameter Karplus equation of the form

  经验 Karplus 方程在柔性分子的构象分析中非常有用，特别是关于碳水化合物。然而，酯官能化碳水化合物的 C(sp2)OCH 二面角并没有被广泛使用的 COCH 二面角的 Karplus 方程很好地描述，因为它们基于 C(sp3)OCH 数据。在此，我们基于 6-O-乙酰-α/ß-D-吡喃葡萄糖的量子力学计算，提出了形式为 JCOCH = 5.18 cos2(*) – 1.42 cos(*) + 1.05 的三参数 Karplus 方程. 该方程在实验确定的 JCH 值与使用 GLYCAM06 力场对一组乙酰化葡萄糖和葡萄糖醛酸甲酯进行 MD 模拟计算得出的值之间给出了令人满意的一致性。
• TMSOTf-Catalyzed Silylation: Streamlined Regioselective One-Pot Protection and Acetylation of Carbohydrates
  作者：A. Abragam Joseph、Ved Prakash Verma、Xin-Yi Liu、Chia-Hui Wu、Vijay M. Dhurandhare、Cheng-Chung Wang

  DOI：10.1002/ejoc.201101267

  日期：2012.2

  A highly efficient TMSOTf-catalyzed HMDS silylation of sugars, which can easily be integrated with subsequent reactions in one-pot fashion, has been developed. Its usefulness was demonstrated by applications to streamlined regioselective one-pot protection and nonenzymatic acetylation of un

  已经开发出一种高效的 TMSOTf 催化的 HMDS 糖基硅烷化，它可以很容易地以一锅法与后续反应相结合。其在简化区域选择性一锅法保护和非酶乙酰化方面的应用证明了其有用性。