phenyl 6-O-benzyl-2,3,4-tri-O-tert-butyldimethylsilyl-1-thio-β-D-glucopyranoside | 947256-83-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 6-O-benzyl-2,3,4-tri-O-tert-butyldimethylsilyl-1-thio-β-D-glucopyranoside
• 英文别名: TBDMS(-2)[TBDMS(-3)][TBDMS(-4)][Bn(-6)]Glc(b)-SPh；[(2R,3R,4S,5R,6S)-3,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2-(phenylmethoxymethyl)-6-phenylsulfanyloxan-4-yl]oxy-tert-butyl-dimethylsilane
• CAS: 947256-83-9
• 化学式: C₃₇H₆₄O₅SSi₃
• 分子量: 705.235
• InChiKey: LEDIXNGVZKZSJG-RUOAZZEASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.89
• 重原子数：
  46
• 可旋转键数：
  15
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  71.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  phenyl 6-O-benzyl-2,3,4-tri-O-tert-butyldimethylsilyl-1-thio-β-D-glucopyranoside 在 三氟甲磺酸 N-碘代丁二酰亚胺 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 phenyl 2,3,4-tri-O-benzyl-6-O-(6-O-benzyl-β-D-glucopyranosyl)-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  “Super Armed” Glycosyl Donors:  Conformational Arming of Thioglycosides by Silylation

  摘要：

  Glycosyl donors protected with bulky silyl protective groups (tert-butyldimethylsilyl, TBS), on the 2-, 3-, and 4-OH groups were found to have superior reactivity compared with benzylated thioglucosides. The enhanced reactivity is explained by the stereoelectronic effects associated with the conformational change induced by the silylation. A TBS silylated thioglucoside donor has axial OR groups, whereas a benzylated thioglucoside has equatorial OR groups, leading to much more favorable charge-dipole interactions in the transition state. This concept could be used to create "super armed" glucosyl, mannosyl, rhamnosyl, and galactosyl donors, which could cross-couple with the armed acceptors, phenyl 2,3,4-tri-O- benzyl-beta-D-thioglucoside or phenyl 2,3,6-tri-O-benzyl-beta-D-thioglucoside, to give the corresponding armed disaccharides in good to excellent yields.

  DOI：

  10.1021/ja071955l
• 作为产物：
  描述：

  1-硫代-b-D-吡喃葡萄糖苷对甲苯酯 在 吡啶 、 4-二甲氨基吡啶 作用下， 反应 24.0h， 生成 phenyl 6-O-benzyl-2,3,4-tri-O-tert-butyldimethylsilyl-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  “Super Armed” Glycosyl Donors:  Conformational Arming of Thioglycosides by Silylation

  摘要：

  Glycosyl donors protected with bulky silyl protective groups (tert-butyldimethylsilyl, TBS), on the 2-, 3-, and 4-OH groups were found to have superior reactivity compared with benzylated thioglucosides. The enhanced reactivity is explained by the stereoelectronic effects associated with the conformational change induced by the silylation. A TBS silylated thioglucoside donor has axial OR groups, whereas a benzylated thioglucoside has equatorial OR groups, leading to much more favorable charge-dipole interactions in the transition state. This concept could be used to create "super armed" glucosyl, mannosyl, rhamnosyl, and galactosyl donors, which could cross-couple with the armed acceptors, phenyl 2,3,4-tri-O- benzyl-beta-D-thioglucoside or phenyl 2,3,6-tri-O-benzyl-beta-D-thioglucoside, to give the corresponding armed disaccharides in good to excellent yields.

  DOI：

  10.1021/ja071955l

文献信息

• Conformationally armed glycosyl donors: reactivity quantification, new donors and one pot reactions
  作者：Christian Marcus Pedersen、Lavinia G. Marinescu、Mikael Bols

  DOI：10.1039/b801305e

  日期：——

  The relative reactivity of conformationally armed thioglycosides is quantified.

  相对反应性被量化为构象性活化的硫代糖苷。
• Superarming of Glycosyl Donors by Combined Neighboring and Conformational Effects
  作者：Mads Heuckendorff、Hemali D. Premathilake、Papapida Pornsuriyasak、Anders Ø. Madsen、Christian M. Pedersen、Mikael Bols、Alexei V. Demchenko

  DOI：10.1021/ol402371b

  日期：2013.9.20

  A novel glycosyl donor that combines the concepts of both conformational and electronic superarming has been synthesized. The reactivity and selectivity of the donor have been tested in competition experiments.
• “Super Armed” Glycosyl Donors:  Conformational Arming of Thioglycosides by Silylation
  作者：Christian Marcus Pedersen、Lars Ulrik Nordstrøm、Mikael Bols

  DOI：10.1021/ja071955l

  日期：2007.7.1

  Glycosyl donors protected with bulky silyl protective groups (tert-butyldimethylsilyl, TBS), on the 2-, 3-, and 4-OH groups were found to have superior reactivity compared with benzylated thioglucosides. The enhanced reactivity is explained by the stereoelectronic effects associated with the conformational change induced by the silylation. A TBS silylated thioglucoside donor has axial OR groups, whereas a benzylated thioglucoside has equatorial OR groups, leading to much more favorable charge-dipole interactions in the transition state. This concept could be used to create "super armed" glucosyl, mannosyl, rhamnosyl, and galactosyl donors, which could cross-couple with the armed acceptors, phenyl 2,3,4-tri-O- benzyl-beta-D-thioglucoside or phenyl 2,3,6-tri-O-benzyl-beta-D-thioglucoside, to give the corresponding armed disaccharides in good to excellent yields.