benzoxazol-2-yl 3,4,6-tri-O-benzoyl-2-O-benzyl-1-thio-β-D-glucopyranoside | 862537-76-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: benzoxazol-2-yl 3,4,6-tri-O-benzoyl-2-O-benzyl-1-thio-β-D-glucopyranoside
• 英文别名: [(2R,3R,4S,5R,6S)-6-(1,3-benzoxazol-2-ylsulfanyl)-3,4-dibenzoyloxy-5-phenylmethoxyoxan-2-yl]methyl benzoate
• CAS: 862537-76-6
• 化学式: C₄₁H₃₃NO₉S
• 分子量: 715.78
• InChiKey: RVSVPXCYEHXKEM-ZSVUXBGXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.7
• 重原子数：
  52
• 可旋转键数：
  15
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  149
• 氢给体数：
  0
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  benzoxazol-2-yl 3,4,6-tri-O-benzoyl-2-O-benzyl-1-thio-β-D-glucopyranoside 、 双丙酮半乳糖 在 5A molecular sieve 、 copper(II) bis(trifluoromethanesulfonate) 作用下， 以 二氯甲烷 为溶剂， 反应 14.0h， 以14%的产率得到6-O-(2'-O-benzyl-3',4',6'-tri-O-benzoyl-α-D-glucopyranosyl)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranoside
  参考文献：
  名称：

  Revisiting the Armed−Disarmed Concept:  The Importance of Anomeric Configuration in the Activation of S-Benzoxazolyl Glycosides

  摘要：

  The unexpectedly high reactivity of a (2-benzoxazolyl) per-O-benzoyl-beta-D-thioglucoside and related donors in reactions promoted by copper(II) trifluoromethanesulfonate is revealed, by comparison with the unreactive alpha-anomer, to be the result of neighboring group participation. Revision of the armed-disarmed concept for glycosyl donors is not required.

  DOI：

  10.1021/ol701466u
• 作为产物：
  描述：

  benzoxazol-2-yl 3,4,6-tri-O-acetyl-2-O-benzyl-1-thio-β-D-glucopyranoside 在 吡啶 、 sodium methylate 作用下， 以 甲醇 、 水 为溶剂， 反应 1.5h， 生成 benzoxazol-2-yl 3,4,6-tri-O-benzoyl-2-O-benzyl-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  回顾武装解除武装的概念原理：化学选择性寡糖合成中的s-苯并恶唑基糖苷。

  摘要：

  [反应：请参见文字]。已经发现2-O-苄基-3,4,6-三-O-酰基SBox糖苷的反应性甚至比“解除武装的”过酰化衍生物低得多。该发现已应用于合成各种寡糖，其单体单元通过顺式-顺式，反式-顺式和顺式-顺式顺序的糖苷键连接。事实证明，在中等程度的（解除）武装（酰化）以及随后的解除武装的（2-O-苄基-3,4-O-二酰化）受体上的两步活化（苄基化）供体也是可行的。

  DOI：

  10.1021/ol050969y

文献信息

• Revisiting the Armed−Disarmed Concept Rationale:  <i>S</i>-Benzoxazolyl Glycosides in Chemoselective Oligosaccharide Synthesis
  作者：Medha N. Kamat、Alexei V. Demchenko

  DOI：10.1021/ol050969y

  日期：2005.7.1

  2-O-benzyl-3,4,6-tri-O-acyl SBox glycosides are significantly less reactive than even "disarmed" peracylated derivatives. This finding has been applied to the synthesis of various oligosaccharides, the monomeric units of which are connected via cis-cis, trans-cis, and cis-trans sequential glycosidic linkages. Two-stage activation of the armed (benzylated) donor over moderately (dis)armed (acylated) and, subsequently

  [反应：请参见文字]。已经发现2-O-苄基-3,4,6-三-O-酰基SBox糖苷的反应性甚至比“解除武装的”过酰化衍生物低得多。该发现已应用于合成各种寡糖，其单体单元通过顺式-顺式，反式-顺式和顺式-顺式顺序的糖苷键连接。事实证明，在中等程度的（解除）武装（酰化）以及随后的解除武装的（2-O-苄基-3,4-O-二酰化）受体上的两步活化（苄基化）供体也是可行的。
• Glycosyl Alkoxythioimidates as Complementary Building Blocks for Chemical Glycosylation
  作者：Sneha C. Ranade、Sophon Kaeothip、Alexei V. Demchenko

  DOI：10.1021/ol1023079

  日期：2010.12.17

  It is reported that S-glycosyl O-methyl phenylcarbamothioates (SNea carbamothioates) have a fully orthogonal character in comparison to S-benzoxazolyl (SBox) glycosides. This complete orthogonality was revealed by performing competitive glycosylation experiments in the presence of various promoters. The results obtained indicate that SNea carbamothioates have a very similar reactivity profile to that of glycosyl thiocyanates, yet are significantly more stable and tolerate selected protecting group manipulations. These features make the SNea carbamothioates new promising building blocks for further utilization in
• Revisiting the Armed−Disarmed Concept:  The Importance of Anomeric Configuration in the Activation of <i>S</i>-Benzoxazolyl Glycosides
  作者：David Crich、Ming Li

  DOI：10.1021/ol701466u

  日期：2007.10.1

  The unexpectedly high reactivity of a (2-benzoxazolyl) per-O-benzoyl-beta-D-thioglucoside and related donors in reactions promoted by copper(II) trifluoromethanesulfonate is revealed, by comparison with the unreactive alpha-anomer, to be the result of neighboring group participation. Revision of the armed-disarmed concept for glycosyl donors is not required.
• <i>S</i>-Benzoxazolyl as a Stable Protecting Moiety and a Potent Anomeric Leaving Group in Oligosaccharide Synthesis
  作者：Medha N. Kamat、Cristina De Meo、Alexei V. Demchenko

  DOI：10.1021/jo071191s

  日期：2007.8.31

  As a part of a program for developing new versatile building blocks for stereoselective glycosylation and convergent oligosaccharide synthesis, we demonstrated that S-benzoxazolyl (SBox) glycosides are stable toward major protecting group manipulations employed in carbohydrate chemistry. On the other hand, they can be glycosidated under relatively mild reaction conditions to afford either 1,2-trans

  作为开发用于立体选择性糖基化和收敛性寡糖合成的新多功能构件的计划的一部分，我们证明了S-苯并恶唑基（SBox）糖苷对碳水化合物化学中采用的主要保护基操作稳定。另一方面，它们可以在相对温和的反应条件下被糖基化以提供1，2-反式或1，2-顺式连接的二糖。还证明了SBox部分的选择性和化学选择性活化是可行的，这通过合成许多寡糖序列得到证明。