3,4,6-tri-O-benzoyl-2-O-benzyl-α-D-glucopyranosyl bromide | 72946-46-4

• 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: 3,4,6-tri-O-benzoyl-2-O-benzyl-α-D-glucopyranosyl bromide
• 英文别名: 2,4,6-Tri-O-benzoyl-2-O-benzyl-α-D-glucopyranosylbromid；[(2R,3R,4S,5R,6R)-3,4-dibenzoyloxy-6-bromo-5-phenylmethoxyoxan-2-yl]methyl benzoate
• CAS: 72946-46-4
• 化学式: C₃₄H₂₉BrO₈
• 分子量: 645.503
• InChiKey: MCWGFUOZSAXGGH-SAEUYMBFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7
• 重原子数：
  43
• 可旋转键数：
  13
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  97.4
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  3,4,6-tri-O-benzoyl-2-O-benzyl-α-D-glucopyranosyl bromide 在 silver carbonate 作用下， 以 水 、 丙酮 为溶剂， 以86%的产率得到1,3,4,6-tetra-O-benzoyl-2-O-benzyl-D-glucopyranose
  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：

  ethyl 3,4,6-tri-O-benzoyl-2-O-benzyl-1-thio-β-D-glucopyranoside 在 溴 作用下， 以 二氯甲烷 为溶剂， 反应 0.25h， 以71%的产率得到3,4,6-tri-O-benzoyl-2-O-benzyl-α-D-glucopyranosyl bromide
  参考文献：
  名称：

  Glycosidation of Thioglycosides in the Presence of Bromine: Mechanism, Reactivity, and Stereoselectivity

  摘要：

  Elaborating on previous studies by Lemieux for highly reactive "armed" bromides, we discovered that beta-bromide of the superdisarmed (2-O-benzyl-3,4,6-tri-O-benzoyl) series can be directly obtained from the thioglycoside precursor. When this bromide is glycosidated, alpha-glycosides form exclusively; however, the yields of such transformations may be low due to the competing anomerization into alpha-bromide that is totally unreactive under the established reaction conditions.

  DOI：

  10.1021/jo2019174

文献信息

• An expedient route to acylated glucosyl halides with a free 2-OH group
  作者：Frieder W. Lichtenthaler、Bernd Köhler

  DOI：10.1016/0008-6215(94)84076-8

  日期：1994.5

  carbonyl group of 3,4,6-tri-O-benzoyl-α- d -arabino-hexosyl-2-ulose bromide (8), readily accessible from the hydroxyglycal ester, can be reduced by cyanoborohydride without affecting the anomeric bromine; exclusive axial attack of the hydride affords the benzoylated glucosyl bromide 6 with a free 2-OH group (72%). This amounts to a five-step synthesis from d -glucose, free from chromatography, in 55% overall

  摘要氰基硼氢化物可还原3,4,6-三-O-苯甲酰基-α-d-阿拉伯糖基己糖基-2-ulose溴化物（8）的羰基，而不会影响端粒溴; 氢化物的唯一轴向侵蚀得到带有游离2-OH基团（72％）的苯甲酰化葡糖基溴化物6。这相当于由d-葡萄糖进行的五步合成，无色谱，总产率为55％。溴化物6，或更具反应性的α-碘化物7，是通过卤素交换从6平稳生成的，容易发生α-或β-选择性糖苷化，强调了它们作为糖基供体的潜力，可用于生成（1→2）连接的寡糖。
• 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.
• Glycosidation of Thioglycosides in the Presence of Bromine: Mechanism, Reactivity, and Stereoselectivity
  作者：Sophon Kaeothip、Jagodige P. Yasomanee、Alexei V. Demchenko

  DOI：10.1021/jo2019174

  日期：2012.1.6

  Elaborating on previous studies by Lemieux for highly reactive "armed" bromides, we discovered that beta-bromide of the superdisarmed (2-O-benzyl-3,4,6-tri-O-benzoyl) series can be directly obtained from the thioglycoside precursor. When this bromide is glycosidated, alpha-glycosides form exclusively; however, the yields of such transformations may be low due to the competing anomerization into alpha-bromide that is totally unreactive under the established reaction conditions.