2'-trimethylsilylethyl β-D-xylopyranoside | 197143-81-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2'-trimethylsilylethyl β-D-xylopyranoside
• 英文别名: (2S,3R,4S,5R)-2-(2-trimethylsilylethoxy)oxane-3,4,5-triol
• CAS: 197143-81-0
• 化学式: C₁₀H₂₂O₅Si
• 分子量: 250.367
• InChiKey: VBLCKZIYIUAEBZ-UTINFBMNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.22
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  79.2
• 氢给体数：
  3
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2'-trimethylsilylethyl β-D-xylopyranoside 在 4-二甲氨基吡啶 、 N-碘代丁二酰亚胺 、 甲磺酰溴 、 三氟甲磺酸 、 MS 300AW 、 四丁基氟化铵 、 sodium methylate 、 silver trifluoromethanesulfonate 、 对甲苯磺酸 、 溶剂黄146 、 三乙胺 、 二异丙胺 作用下， 以 吡啶 、 氯仿 、 水 为溶剂， 反应 90.75h， 生成 methyl (2S,4S,5R,6R)-5-acetamido-4-acetyloxy-2-[(2R,3S,4S,5R,6S)-5-acetyloxy-2-(acetyloxymethyl)-6-[(3R,4S,5R,6S)-4,5-diacetyloxy-6-(2-trimethylsilylethoxy)oxan-3-yl]oxy-3-hydroxyoxan-4-yl]oxy-6-[(1S,2R)-1,2,3-triacetyloxypropyl]oxane-2-carboxylate
  参考文献：
  名称：

  Synthesis of XylβCer, Galβ1−4XylβCer, NeuAcα2−3Galβ1−4XylβCer and the Corresponding Lactone and Lactam Trisaccharides

  摘要：

  2-(Trimethylsilyl)ethyl 2-O-benzoyl- and 2,3-di-O-acetyl-beta-D-xylopyranosides (12 and 14) were synthesized in high yields and subjected to glycosylation with various glycosyl donors. Galactosylation of 12 gave the xylose analogue of TMSEt lactoside (3), which was transformed into the glycosyl acceptor 19. Sialylation then gave the xylose analogue of G(M3) trisaccharide (5). The TMSEt glycosides 10, 25, and 32 were transformed into the corresponding trichloroacetimidates, which were used for glycosylation of an azidosphingosine derivative. The resulting sphingosyl glycosides were transformed into the title ceramides. Treatment of NeuAc alpha 2-3Gal beta 1-4Xyl beta Cer (5) with acetic acid gave the corresponding l''-2'-lactone 7. Glycosylation of 12 or 14 with a G(M4)-lactam donor (40) gave the xylose analogue of G(M3)-lactam (42). There was a 3-fold increase in the formation of GAG chains in the presence of 0.5 mu M Xyl beta Cer (2) in the medium.

  DOI：

  10.1021/jo970298k
• 作为产物：
  描述：

  2,3,4-三-O-乙酰基-α-D-木吡喃糖苷溴 在 calcium sulfate 、 sodium 、 mercury(I) bromide 、 mercury(II) oxide 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 50.08h， 生成 2'-trimethylsilylethyl β-D-xylopyranoside
  参考文献：
  名称：

  The synthesis of a carbohydrate-like dihydrooxazine and tetrahydrooxazine as putative inhibitors of glycoside hydrolases: A direct synthesis of isofagomine

  摘要：

  将苯甲基2,3-O-异丙基甲醚-β-L-木糖苷在Mitsunobu条件下与N-羟基邻苯二甲酰亚胺反应，随后进行保护基交换，得到苯甲基4-O-[(叔丁氧羰基)氨基]-2,3-O-异丙基甲醚-α-D-阿拉伯糖苷。经轻酸水解和催化氢解后，得到4-O-[(叔丁氧羰基)氨基]-D-阿拉伯糖，加热水后，得到二氢噁嗪[(4R,5S,6R)-5,6-二氢-4,5-二羟基-6-羟甲基-4H-1,2-噁嗪]，为结晶固体。该固体的单晶结构测定显示其存在于⁵H₆构象。对二氢噁嗪进行还原得到四氢噁嗪[(4R,5S,6R)-4,5-二羟基-6-羟甲基-3,4,5,6-四氢-2H-1,2-噁嗪]。二氢噁嗪是两种β-葡萄糖苷酶的有效抑制剂(K_i=27和35 µM)。苯甲基2,3-O-异丙基甲醚-β-L-木糖苷通过衍生的咪唑酸酯转化为一个腈，经还原和保护基操作后，得到苯甲基4-C-氨甲基-4-脱氧-α-D-阿拉伯糖苷。处理这种胺与氢和钯-碳后得到异法戈胺。关键词：二氢噁嗪，四氢噁嗪，异法戈胺，亚胺糖，糖苷酶抑制剂。

  DOI：

  10.1139/v02-060

文献信息

• The synthesis of a carbohydrate-like dihydrooxazine and tetrahydrooxazine as putative inhibitors of glycoside hydrolases: A direct synthesis of isofagomine
  作者：Wayne M Best、James M Macdonald、Brian W Skelton、Robert V Stick、D Matthew G Tilbrook、Allan H White

  DOI：10.1139/v02-060

  日期：2002.8.1

  The treatment of benzyl 2,3-O-isopropylidene-β-L-xylopyranoside with N-hydroxyphthalimide under Mitsunobu conditions, followed by protecting-group interchange, gave benzyl 4-O-[(tert-butoxycarbonyl)amino]-2,3- O-isopropylidene-α-D-arabinoside. Mild acid hydrolysis and catalytic hydrogenolysis afforded 4-O-[(tert-butoxycarbonyl)amino]-D-arabinose that, upon heating in water, gave the dihydrooxazine [(4R,5S,6R)-5,6-dihydro-4,5-dihydroxy-6-hydroxymethyl-4H-1,2-oxazine] as a crystalline solid. A single-crystal structure determination of this solid showed it to exist in the ⁵H₆ conformation. Reduction of the dihydrooxazine gave the tetrahydrooxazine [(4R,5S,6R)-4,5-dihydroxy-6-hydroxymethyl-3,4,5,6-tetrahydro-2H-1,2-oxazine]. The dihydrooxazine was an effective inhibitor of two β-glucosidases (K_i = 27 and 35 µM). Benzyl 2,3-O-isopropylidene-β-L-xylopyranoside, via the derived imidazylate, was converted into a nitrile that, upon reduction and protecting-group manipulations, gave benzyl 4-C-aminomethyl-4-deoxy-α-D-arabinoside. Treatment of this amine with hydrogen and palladium-on-carbon gave isofagomine.Key words: dihydrooxazine, tetrahydrooxazine, isofagomine, iminosugars, glycosidase inhibitors.

  将苯甲基2,3-O-异丙基甲醚-β-L-木糖苷在Mitsunobu条件下与N-羟基邻苯二甲酰亚胺反应，随后进行保护基交换，得到苯甲基4-O-[(叔丁氧羰基)氨基]-2,3-O-异丙基甲醚-α-D-阿拉伯糖苷。经轻酸水解和催化氢解后，得到4-O-[(叔丁氧羰基)氨基]-D-阿拉伯糖，加热水后，得到二氢噁嗪[(4R,5S,6R)-5,6-二氢-4,5-二羟基-6-羟甲基-4H-1,2-噁嗪]，为结晶固体。该固体的单晶结构测定显示其存在于⁵H₆构象。对二氢噁嗪进行还原得到四氢噁嗪[(4R,5S,6R)-4,5-二羟基-6-羟甲基-3,4,5,6-四氢-2H-1,2-噁嗪]。二氢噁嗪是两种β-葡萄糖苷酶的有效抑制剂(K_i=27和35 µM)。苯甲基2,3-O-异丙基甲醚-β-L-木糖苷通过衍生的咪唑酸酯转化为一个腈，经还原和保护基操作后，得到苯甲基4-C-氨甲基-4-脱氧-α-D-阿拉伯糖苷。处理这种胺与氢和钯-碳后得到异法戈胺。关键词：二氢噁嗪，四氢噁嗪，异法戈胺，亚胺糖，糖苷酶抑制剂。
• Synthesis of XylβCer, Galβ1−4XylβCer, NeuAcα2−3Galβ1−4XylβCer and the Corresponding Lactone and Lactam Trisaccharides
  作者：Michael Wilstermann、Göran Magnusson

  DOI：10.1021/jo970298k

  日期：1997.11.1

  2-(Trimethylsilyl)ethyl 2-O-benzoyl- and 2,3-di-O-acetyl-beta-D-xylopyranosides (12 and 14) were synthesized in high yields and subjected to glycosylation with various glycosyl donors. Galactosylation of 12 gave the xylose analogue of TMSEt lactoside (3), which was transformed into the glycosyl acceptor 19. Sialylation then gave the xylose analogue of G(M3) trisaccharide (5). The TMSEt glycosides 10, 25, and 32 were transformed into the corresponding trichloroacetimidates, which were used for glycosylation of an azidosphingosine derivative. The resulting sphingosyl glycosides were transformed into the title ceramides. Treatment of NeuAc alpha 2-3Gal beta 1-4Xyl beta Cer (5) with acetic acid gave the corresponding l''-2'-lactone 7. Glycosylation of 12 or 14 with a G(M4)-lactam donor (40) gave the xylose analogue of G(M3)-lactam (42). There was a 3-fold increase in the formation of GAG chains in the presence of 0.5 mu M Xyl beta Cer (2) in the medium.