(6-styryl-pyridin-2-yl)-di-p-tolyl-methanol | 539836-40-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (6-styryl-pyridin-2-yl)-di-p-tolyl-methanol
• CAS: 539836-40-3
• 化学式: C₂₈H₂₇NO
• 分子量: 393.528
• InChiKey: CSYOLGDLNUZFIN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.77
• 重原子数：
  30.0
• 可旋转键数：
  6.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  33.12
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (6-styryl-pyridin-2-yl)-di-p-tolyl-methanol 在 吡啶 、 盐酸 作用下， 以 水 为溶剂， 反应 96.0h， 生成 methyl 6-O-(6-phenethyl-pyridin-2-yl)-di-p-tolyl-methyl-α-D-glucopyranoside
  参考文献：
  名称：

  Directing-protecting groups for carbohydrates. Design, conformational study, synthesis and application to regioselective functionalization

  摘要：

  A novel concept of regioselective transformation of secondary hydroxyl groups in carbohydrates is presented. First, the relative reactivity of the free hydroxyl groups of onoprotected D-glucose derivatives was assessed using acetylation as a model reaction. As a result, acylation of these polyols gave it mixture of monosubstituted products in which the 3-O functionalized derivatives predominated. Novel hydrogen bond acceptor protecting groups were next designed to modulate the 4-OH and 3-OH reactivity in the hope to mediate higher regioselective transformations. A molecular modeling study later validated by spectroscopic analysis predicted additional intramolecular hydrogen bonds between the hydroxyl groups and pyridyl-containing protecting groups. Taking advantage of this induced hydrogen bond network. we achieved regioselective acetylation of the hydroxyl group at position 3 without protecting any secondary hydroxyl groups of the carbohydrate moiety. This designed protecting/directing group increased the nucleophilicity and the steric hindrance of position 3. As a result, optimization of the reaction conditions enabled the monoacetylation (not affected by steric hindrance) of 6-O-protected,glucopyranosides at position 3 and selective silylation (affected by steric hindrance) of position 2 in high isolated yields and regioselectivities. This result certainly opens doors to the regioselective open glycosylation of carbohydrates. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.04.060
• 作为产物：
  描述：

  吡啶-2.6-二羧酸二甲酯 在 palladium on activated charcoal 、 lithium aluminium tetrahydride 、 正丁基锂 、 N-苯基双(三氟甲烷磺酰)亚胺 、 氢气 、 sodium hexamethyldisilazane 作用下， 以 四氢呋喃 、 乙醇 、 正戊烷 为溶剂， 反应 6.0h， 生成 (6-styryl-pyridin-2-yl)-di-p-tolyl-methanol
  参考文献：
  名称：

  Directing-protecting groups for carbohydrates. Design, conformational study, synthesis and application to regioselective functionalization

  摘要：

  A novel concept of regioselective transformation of secondary hydroxyl groups in carbohydrates is presented. First, the relative reactivity of the free hydroxyl groups of onoprotected D-glucose derivatives was assessed using acetylation as a model reaction. As a result, acylation of these polyols gave it mixture of monosubstituted products in which the 3-O functionalized derivatives predominated. Novel hydrogen bond acceptor protecting groups were next designed to modulate the 4-OH and 3-OH reactivity in the hope to mediate higher regioselective transformations. A molecular modeling study later validated by spectroscopic analysis predicted additional intramolecular hydrogen bonds between the hydroxyl groups and pyridyl-containing protecting groups. Taking advantage of this induced hydrogen bond network. we achieved regioselective acetylation of the hydroxyl group at position 3 without protecting any secondary hydroxyl groups of the carbohydrate moiety. This designed protecting/directing group increased the nucleophilicity and the steric hindrance of position 3. As a result, optimization of the reaction conditions enabled the monoacetylation (not affected by steric hindrance) of 6-O-protected,glucopyranosides at position 3 and selective silylation (affected by steric hindrance) of position 2 in high isolated yields and regioselectivities. This result certainly opens doors to the regioselective open glycosylation of carbohydrates. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.04.060

文献信息

• Modulation of the relative reactivities of carbohydrate secondary hydroxyl groups. Modification of the hydrogen bond network
  作者：Nicolas Moitessier、Yves Chapleur

  DOI：10.1016/s0040-4039(03)00141-2

  日期：2003.2

  An approach towards the control of the relative regioselectivity of the secondary hydroxyl groups is presented. Original protecting groups, which are capable of specific intramolecular hydrogen bonds and are likely to modulate the partial charges of the oxygen atoms, have been developed. Qualitative NMR experiments confirmed the existence of the expected hydrogen bonds and shed light on the perturbation of the cooperative intramolecular hydrogen bond network. Further reactivity studies are presented and confirm the potential of protecting group-mediated regioselective functionalization of carbohydrates. (C) 2003 Elsevier Science Ltd. All rights reserved.