phenyl 3,4,6-tri-O-benzyl-2-O-(o-cyanobenzyl)-1-thio-β-D-glucopyranoside

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 3,4,6-tri-O-benzyl-2-O-(o-cyanobenzyl)-1-thio-β-D-glucopyranoside
• 英文别名: phenyl 3,4,6-tri-O-benzyl-2-O-(2-cyanobenzyl)-β-D-1-thio-glucopyranoside；Phenyl 2-O-(o-cyano)benzyl-3,4,6-tri-O-benzyl-beta-D-thioglucopyranoside；2-[[(2S,3R,4S,5R,6R)-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-2-phenylsulfanyloxan-3-yl]oxymethyl]benzonitrile
• 化学式: C₄₁H₃₉NO₅S
• 分子量: 657.83
• InChiKey: HKZUEHZOYAYDHS-WEOXEBIHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.6
• 重原子数：
  48
• 可旋转键数：
  15
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  95.2
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  phenyl 3,4,6-tri-O-benzyl-2-O-(o-cyanobenzyl)-1-thio-β-D-glucopyranoside 、 1-壬醇 在 2,4,6-三叔丁基吡啶 、 三氟甲磺酸酐 、 二苯基亚砜 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 3.5h， 以54%的产率得到nonyl 3,4,6-tri-O-benzyl-2-O-(o-cyanobenzyl)-β-D-glucopyranoside
  参考文献：
  名称：

  Application of 2-Substituted Benzyl Groups in Stereoselective Glycosylation

  摘要：

  The use of 2-O-(2-nitrobenzyl) and 2-O-(2-cyanobenzyl) groups controls stereoselective formation of 1,2-trans-glycosidic linkages via the arming participation effect. The observed stereoselectivity likely arises from the intramolecular formation of cyclic intermediate between the electron-rich substituent and the donor oxacarbenium ion providing the expected facial selectivity for attack of the glycoside acceptor. The stereodirecting effect of the 2-nitro- and 2-cyanobenzyl groups attached at the remote position (C-3, C-4, and C-6) of the donor molecule have also been investigated. To prove the postulated mechanism based on the participation effect of 2-substituted benzyl groups in the glycosylation stereoselectivity we used DFT theoretical calculation methodology.

  DOI：

  10.1021/jo502186f
• 作为产物：
  描述：

  phenyl 3,4,6-tri-O-benzyl-2-O-acetyl-1-thio-β-D-glucopyranoside 在 potassium cyanide 、 sodium hydride 作用下， 以 甲醇 、 乙腈 、 mineral oil 为溶剂， 反应 4.5h， 生成 phenyl 3,4,6-tri-O-benzyl-2-O-(o-cyanobenzyl)-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  Application of 2-Substituted Benzyl Groups in Stereoselective Glycosylation

  摘要：

  The use of 2-O-(2-nitrobenzyl) and 2-O-(2-cyanobenzyl) groups controls stereoselective formation of 1,2-trans-glycosidic linkages via the arming participation effect. The observed stereoselectivity likely arises from the intramolecular formation of cyclic intermediate between the electron-rich substituent and the donor oxacarbenium ion providing the expected facial selectivity for attack of the glycoside acceptor. The stereodirecting effect of the 2-nitro- and 2-cyanobenzyl groups attached at the remote position (C-3, C-4, and C-6) of the donor molecule have also been investigated. To prove the postulated mechanism based on the participation effect of 2-substituted benzyl groups in the glycosylation stereoselectivity we used DFT theoretical calculation methodology.

  DOI：

  10.1021/jo502186f

文献信息

• Efficient Synthesis of 2-OH Thioglycosides from Glycals Based on the Reduction of Aryl Disulfides by NaBH4
  作者：Yang-Fan Guo、Tao Luo、Guang-Jing Feng、Chun-Yang Liu、Hai Dong

  DOI：10.3390/molecules27185980

  日期：——

  An improved method to efficiently synthesize 2-OH thioaryl glycosides starting from corresponding per-protected glycals was developed, where 1,2-anhydro sugars were prepared by the oxidation of glycals with oxone, followed by reaction of crude crystalline 1,2-anhydro sugars with NaBH4 and aryl disulfides. This method has been further used in a one-pot reaction to synthesize glycosyl donors having both

  开发了一种从相应的过保护糖苷开始有效合成 2-OH 硫代芳基糖苷的改进方法，其中 1,2-脱水糖是通过糖醛与过氧化氢进行氧化，然后与粗结晶 1,2-脱水糖反应制备的。与 NaBH 4和芳基二硫化物。该方法已进一步用于一锅反应，以合成具有“武装”和“NGP（邻接组参与）”效应的糖基供体。