3-O-tert-butyldiphenylsilyl-1,2,5,6-di-O-isopropylidene-α-D-glucofuranose | 853399-79-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-O-tert-butyldiphenylsilyl-1,2,5,6-di-O-isopropylidene-α-D-glucofuranose
• 英文别名: [(3aR,5R,6S,6aR)-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-6-yl]oxy-tert-butyl-diphenylsilane
• CAS: 853399-79-8
• 化学式: C₂₈H₃₈O₆Si
• 分子量: 498.692
• InChiKey: UTRYLOLZKRHOQM-NHTNDUFYSA-N

物化性质

• 沸点：
  516.1±50.0 °C(Predicted)
• 密度：
  1.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.96
• 重原子数：
  35
• 可旋转键数：
  6
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  55.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3-O-tert-butyldiphenylsilyl-1,2,5,6-di-O-isopropylidene-α-D-glucofuranose 在 吡啶 、 氢氟酸 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 20.0 ℃ 、999.99 MPa 条件下， 反应 12.0h， 以69%的产率得到双丙酮葡萄糖
  参考文献：
  名称：

  Desilylation under high pressure

  摘要：

  Cleavage of tert-butyldiphenylsilyl (TBDPS) ether was examined under high pressure conditions (1.0 GPa) using HF pyridine in DMF. This method proved to be exceptionally suitable for deprotecting the TBDPS group that resides at the sterically hindered position. Under these conditions, various types of other hydroxyl protecting groups (i.e. benzyl, p-methoxybenzyl, trityl, isopropylidene, cyclohexylidene, allyl, phthaloyl) as well as O- and S-glycosidic linkages were preserved. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(02)00538-5
• 作为产物：
  描述：

  叔丁基二苯基氯硅烷 、 双丙酮葡萄糖 在 N-甲基咪唑 、 碘 作用下， 以 四氢呋喃 为溶剂， 反应 14.0h， 以91%的产率得到3-O-tert-butyldiphenylsilyl-1,2,5,6-di-O-isopropylidene-α-D-glucofuranose
  参考文献：
  名称：

  通过有机棉催化立体选择性合成1,1'-二糖。

  摘要：

  在三环硼酸催化剂存在下，通过使用1,2-二羟基糖基受体和糖基供体可以实现1,1'-二糖的高度立体选择性合成。在该反应中，二醇和催化剂的络合对于糖基供体的活化以及产物的1,2-顺式构型至关重要。糖基供体的异头立体化学取决于所用的糖基供体。还描述了产生的1,1'-二糖的应用。

  DOI：

  10.1002/anie.202004476

文献信息

• Phosphomolybdic Acid Supported on Silica Gel: An Efficient, Mild and Reusable Catalyst for the Chemoselective Hydrolysis of Acetonides
  作者：J. S. Yadav、S. Raghavendra、M. Satyanarayana、E. Balanarsaiah

  DOI：10.1055/s-2005-872701

  日期：——

  Carbohydrate acetonides were chemoselectively cleaved to the corresponding diols by using environmentally benign phosphomolybdic acid (H3PMo12O40) supported on silica gel (PMA-SiO2) at ambient temperature in a short span of 5-7 minutes in acetonitrile. Acid-labile protective groups such as THP, TBS, TBDPS, MOM, OMe and PMB were found to be stable under the reaction conditions.

  碳水化合物乙缩醛在环境友好的负载型磷钼酸（H3PMo12O40/硅胶，简称PMA-SiO2）作用下，于室温、乙腈溶液中仅需5至7分钟即可选择性地裂解为相应的二醇。在这种反应条件下，如THP、TBS、TBDPS、MOM、OMe和PMB等对酸不稳定的保护基团均能保持稳定。
• Iodine-promoted silylation of alcohols with silyl chlorides. Synthetic and mechanistic studies
  作者：Agnieszka Bartoszewicz、Marcin Kalek、Jacek Stawinski

  DOI：10.1016/j.tet.2008.06.070

  日期：2008.9

  An efficient silylating system for 1 degrees, 2 degrees, and 3 degrees, alcohols, consisting of a silyl chloride/N-methylimidazole/iodine, was developed. Synthetic and mechanistic aspects of this new reagent system, and particularly the role of iodine were investigated in detail using H-1 NMR spectroscopy. (C) 2008 Elsevier Ltd. All rights reserved.
• Formal synthesis of (+)-varitriol. Application of Pd(II)/Cu(II)-catalysed bicyclisation of unsaturated polyols
  作者：Miroslav Palík、Oľga Karlubíková、Daniela Lackovičová、Angelika Lásiková、Tibor Gracza

  DOI：10.1016/j.tet.2010.04.074

  日期：2010.7

  A formal and improved synthesis of natural (+)-varitriol from D-glucose and dimethyl L-tartrate, respectively, are reported. The key steps are the Pd(II)/Cu(II)-catalysed bicyclisation of O-benzyl protected triols L-xylo-15 and L-xylo-15/L-lyxo-15, respectively, followed by ring opening of intermediate dianhydro-L-gulitol 16. The syntheses of key intermediate of the furanoside portion 17 proceed in 13 steps with 5% (from bisacetone-D-glucose), and in 12 steps with 7.6% over-all yield from dimethyl L-tartrate, respectively. (C) 2010 Elsevier Ltd. All rights reserved.
• Stereoselective Synthesis of 1,1′‐Disaccharides by Organoboron Catalysis
  作者：Sanae Izumi、Yusuke Kobayashi、Yoshiji Takemoto

  DOI：10.1002/anie.202004476

  日期：2020.8.10

  2‐dihydroxyglycosyl acceptors and glycosyl donors in the presence of a tricyclic borinic acid catalyst. In this reaction, the complexation of the diols and the catalyst is crucial for the activation of glycosyl donors, as well as for the 1,2‐cis‐configuration of the products. The anomeric stereochemistry of the glycosyl donor depends on the employed glycosyl donor. Applications of the produced 1,1′‐disaccharides are

  在三环硼酸催化剂存在下，通过使用1,2-二羟基糖基受体和糖基供体可以实现1,1'-二糖的高度立体选择性合成。在该反应中，二醇和催化剂的络合对于糖基供体的活化以及产物的1,2-顺式构型至关重要。糖基供体的异头立体化学取决于所用的糖基供体。还描述了产生的1,1'-二糖的应用。
• Desilylation under high pressure
  作者：Ichiro Matsuo、Megumi Wada、Yukishige Ito

  DOI：10.1016/s0040-4039(02)00538-5

  日期：2002.4

  Cleavage of tert-butyldiphenylsilyl (TBDPS) ether was examined under high pressure conditions (1.0 GPa) using HF pyridine in DMF. This method proved to be exceptionally suitable for deprotecting the TBDPS group that resides at the sterically hindered position. Under these conditions, various types of other hydroxyl protecting groups (i.e. benzyl, p-methoxybenzyl, trityl, isopropylidene, cyclohexylidene, allyl, phthaloyl) as well as O- and S-glycosidic linkages were preserved. (C) 2002 Elsevier Science Ltd. All rights reserved.