alpha,alpha-二(4-甲基苯基)-吡啶-2-基-甲醇 | 5467-89-0

• 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
• 中文名称: alpha,alpha-二(4-甲基苯基)-吡啶-2-基-甲醇
• 英文名称: bis(4-methylphenyl)-2-pyridylmethanol
• 英文别名: [2]Pyridyl-di-p-tolyl-methanol；Bis(4-methylphenyl)-pyridin-2-ylmethanol
• CAS: 5467-89-0
• 化学式: C₂₀H₁₉NO
• 分子量: 289.377
• InChiKey: FPIMNMKNIFZJKX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  33.1
• 氢给体数：
  1
• 氢受体数：
  2

安全信息

• 海关编码：
  2933399090

反应信息

• 作为反应物：
  描述：

  alpha,alpha-二(4-甲基苯基)-吡啶-2-基-甲醇 在 吡啶 、 氯化亚砜 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 53.0h， 生成 (2R,3S,4S,5R,6S)-2-[[bis(4-methylphenyl)-pyridin-2-ylmethoxy]methyl]-6-methoxyoxane-3,4,5-triol
  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：

  2-吡啶甲酸乙酯 、 对溴甲苯 在 碘 、 magnesium 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 alpha,alpha-二(4-甲基苯基)-吡啶-2-基-甲醇
  参考文献：
  名称：

  An efficient synthesis of pyrido[1,2-a]indoles through aza-Nazarov type cyclization

  摘要：

  通过使用甲酸介导的过渡金属无机酸催化合成，已经开发出一种通过可获得的二芳基(2-吡啶基)甲醇进行氮杂Nazarov型环化反应，合成具有生物学和药用重要性的吡啶[1,2-a]吲哚、吲哚[1,2-a]喹啉和嘧啶[1,2-a]吲哚衍生物的方法。

  DOI：

  10.1039/c4cc08783f

文献信息

• Iron-Catalyzed C-H Bond Functionalization for the Exclusive Synthesis of Pyrido[1,2-<i>a</i>]indoles or Triarylmethanols
  作者：Iyyanar Karthikeyan、Govindasamy Sekar

  DOI：10.1002/ejoc.201403233

  日期：2014.12

  The efficient and selective iron-catalyzed C–H activation of 2-benzhydrylpyridine derivatives was employed for the preparation of pyrido[1,2-a]indoles through an intramolecular C–H amination reaction. In the presence of molecular oxygen as the sole oxidant, the same 2-benzhydrylpyridines were also used for the synthesis of the corresponding tertiary alcohols. In these approaches, the iron catalyst

  2-二苯甲基吡啶衍生物的高效和选择性铁催化C-H活化用于通过分子内C-H胺化反应制备吡啶并[1,2-a]吲哚。在分子氧作为唯一氧化剂的存在下，同样的 2-二苯甲基吡啶也用于合成相应的叔醇。在这些方法中，铁催化剂用于选择性激活 2-二苯甲基吡啶的 C(sp2)-H 键，在分子内闭环 C-H 胺化反应的情况下，吡啶氮原子是一个导向基团，如以及亲核试剂和相同化合物的 C(sp3)-H 键，在氧化反应的情况下，得到相应的三芳基甲醇。
• PdII-Catalyzed Enantioselective Activation of C(sp2)H and C(sp3)H Bonds Using Monoprotected Amino Acids as Chiral Ligands
  作者：Bing-Feng Shi、Nathan Maugel、Yang-Hui Zhang、Jin-Quan Yu

  DOI：10.1002/anie.200801030

  日期：2008.6.16
• Central Stimulants. α,α-Disubstituted 2-Piperidinemethanols and 1,1-Disubstituted Heptahydroöxazolo [3,4-a]pyridines
  作者：Frederick J. McCarty、Charles H. Tilford、M. G. Van Campen

  DOI：10.1021/ja01559a066

  日期：1957.1
• An efficient synthesis of pyrido[1,2-a]indoles through aza-Nazarov type cyclization
  作者：Iyyanar Karthikeyan、Dhanarajan Arunprasath、Govindasamy Sekar

  DOI：10.1039/c4cc08783f

  日期：——

  Transition metal free Brønsted acid mediated synthesis of pyrido[1,2-a]indole scaffolds has been developed through aza-Nazarov type cyclization of readily available diaryl(2-pyridyl)methanol using formic acid for the synthesis of biologically and medicinally important pyrido[1,2-a]indole, indolo[1,2-a]quinoline and pyrimido[1,2-a]indole derivatives.

  通过使用甲酸介导的过渡金属无机酸催化合成，已经开发出一种通过可获得的二芳基(2-吡啶基)甲醇进行氮杂Nazarov型环化反应，合成具有生物学和药用重要性的吡啶[1,2-a]吲哚、吲哚[1,2-a]喹啉和嘧啶[1,2-a]吲哚衍生物的方法。
• Directing-protecting groups for carbohydrates. Design, conformational study, synthesis and application to regioselective functionalization
  作者：Nicolas Moitessier、Pablo Englebienne、Yves Chapleur

  DOI：10.1016/j.tet.2005.04.060

  日期：2005.7

  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.