methyl 2,3,4,6-tetrakis-O-(tert-butyldimethylsilyl)-α-D-glucopyranoside | 116144-10-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,3,4,6-tetrakis-O-(tert-butyldimethylsilyl)-α-D-glucopyranoside
• 英文别名: methyl 2,3,4,6-tetra-O-tert-butyldimethylsilyl-α-D-glucopyranoside；TBDMS(-2)[TBDMS(-3)][TBDMS(-4)][TBDMS(-6)]a-Glc1Me；[(2R,3R,4S,5R,6S)-3,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-6-methoxyoxan-4-yl]oxy-tert-butyl-dimethylsilane
• CAS: 116144-10-6
• 化学式: C₃₁H₇₀O₆Si₄
• 分子量: 651.235
• InChiKey: CLDPSINVZRPNOV-SEFGFODJSA-N

物化性质

• 沸点：
  535.6±50.0 °C(Predicted)
• 密度：
  0.93±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  9.55
• 重原子数：
  41
• 可旋转键数：
  14
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  methyl 2,3,4,6-tetrakis-O-(tert-butyldimethylsilyl)-α-D-glucopyranoside 在 vanadyl trifluoromethanesulfonate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 40.0h， 以88%的产率得到alpha-甲基葡萄糖甙
  参考文献：
  名称：

  Removal of Acid-Labile Protecting Groups on Carbohydrates Using Water-Tolerant and Recoverable Vanadyl Triflate Catalyst

  摘要：

  Acetal, trityl, and TBDMS protecting groups on saccharides were subjected to alcoholysis using a catalytic amount of vanadyl triflate in an MeOH-CH2Cl2 solvent system. The configuration at the anomeric positions of saccharides was retained, and no glycosidic bond cleavage and oxidation of sulfides were observed. The presented method was easily implemented, compatible with diverse functional groups, and regioselective in some cases.

  DOI：

  10.1021/jo061881g
• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 、 alpha-甲基葡萄糖甙 在 吡啶 、 silver nitrate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 30.0h， 以72%的产率得到methyl 2,3,4,6-tetrakis-O-(tert-butyldimethylsilyl)-α-D-glucopyranoside
  参考文献：
  名称：

  Operationally Simple and Efficient Workup Procedure for TBAF-Mediated Desilylation:  Application to Halichondrin Synthesis

  摘要：

  An operationally simple and efficient workup method for tetrabutylammonium fluoride (TBAF)-mediated t-butyldimethylsilyl (TBS) deprotection has been developed. The procedure includes addition of a sulfonic acid resin and calcium carbonate, followed by filtration and evaporation. This method eliminates the tedious aqueous-phase extraction process to remove excess TBAF and materials derived from TBAF, thereby making the protocol highly amenable to multiple TBS deprotections. Its efficiency and usefulness were demonstrated by using the transformation of 1a to 3a in the halichondrin synthesis.

  DOI：

  10.1021/ol063113h

文献信息

• Chemoselective deprotection of acid labile primary hydroxyl protecting groups under CBr4-photoirradiation conditions
  作者：Ming-Yi Chen、Laxmikant N. Patkar、Kuo-Cheng Lu、Adam Shih-Yuan Lee、Chun-Cheng Lin

  DOI：10.1016/j.tet.2004.09.095

  日期：2004.12

  The CBr4-photoirradiation in methanol generates a controlled source of HBr, which can chemoselectively deprotect commonly used hydroxyl-protecting groups in saccharides and nucleosides, such as tert-butyldimethylsilyl, isopropylidene, benzylidene and triphenyl ethers in the presence of other acid-labile functional groups. (C) 2004 Elsevier Ltd. All rights reserved.
• Chemoselective deprotection of primary tert-butyldimethylsilyl ethers on carbohydrate molecules in the presence of secondary silyl ethers
  作者：Ming-Yi Chen、Kuo-Cheng Lu、Adam Shih-Yuan Lee、Chun-Cheng Lin

  DOI：10.1016/s0040-4039(02)00385-4

  日期：2002.4

  The primary silyl ethers of TBDMS-protected saccharides were regioselectively cleaved in excellent yields (71-95%) by treating the silyl ethers with a catalytic amount of CBr4 in methanol under photochemical reaction conditions. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Studies of the selective silylation of methyl α- and β-d-aldohexopyranosides: stability of the partially protected derivatives in polar solvents
  作者：Thérèse Halmos、Roland Montserret、Jean Filippi、Kostas Antonakis

  DOI：10.1016/0008-6215(87)85005-x

  日期：1987.12

  Treatment of methyl .alpha.- (1) and .beta.-D-glucopyranosides, methyl .alpha.- (3) and .beta.-D-galactopyranosides, and methyl .alpha.-D-mannopyranoside (5) with 2, 3, or 4 mol. equiv. of tert-butyldimethylsilyl (TBDMS) chloride under two conditions afforded mixtures of TBDMS ethers which were identified. The following compounds were isolated in synthetically useful yields, the 2,6-di-TBDMS ether of 1 (70%), the 2,6-di- and 2,3,6-tri-TBDMS ethers of 3 (84% and 57%, respectively), and the 2,6-di- and 3,6-di-TBDMS ethers of 5 (50% and 80%, respectively). In dipolar solvents, no migration of the TBDMS groups was detected between partially silylated hydroxyl groups, but the addition of a base (triethylamine or imidazole) caused migration to vicinal cis positions.
• Removal of Acid-Labile Protecting Groups on Carbohydrates Using Water-Tolerant and Recoverable Vanadyl Triflate Catalyst
  作者：Ming-Chung Yan、Yeng-Nan Chen、Huan-Ting Wu、Chang-Ching Lin、Chien-Tien Chen、Chun-Cheng Lin

  DOI：10.1021/jo061881g

  日期：2007.1.1

  Acetal, trityl, and TBDMS protecting groups on saccharides were subjected to alcoholysis using a catalytic amount of vanadyl triflate in an MeOH-CH2Cl2 solvent system. The configuration at the anomeric positions of saccharides was retained, and no glycosidic bond cleavage and oxidation of sulfides were observed. The presented method was easily implemented, compatible with diverse functional groups, and regioselective in some cases.
• Operationally Simple and Efficient Workup Procedure for TBAF-Mediated Desilylation:  Application to Halichondrin Synthesis
  作者：Yosuke Kaburagi、Yoshito Kishi

  DOI：10.1021/ol063113h

  日期：2007.2.1

  An operationally simple and efficient workup method for tetrabutylammonium fluoride (TBAF)-mediated t-butyldimethylsilyl (TBS) deprotection has been developed. The procedure includes addition of a sulfonic acid resin and calcium carbonate, followed by filtration and evaporation. This method eliminates the tedious aqueous-phase extraction process to remove excess TBAF and materials derived from TBAF, thereby making the protocol highly amenable to multiple TBS deprotections. Its efficiency and usefulness were demonstrated by using the transformation of 1a to 3a in the halichondrin synthesis.