2-(hydroxy-phenyl-methyl)-2-methyl-cyclopentanone

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-(hydroxy-phenyl-methyl)-2-methyl-cyclopentanone
• 英文别名: 2-(hydroxy(phenyl)methyl)-2-methylcyclopentan-1-one；(2S)-2-[(S)-hydroxy(phenyl)methyl]-2-methylcyclopentan-1-one
• 化学式: C₁₃H₁₆O₂
• 分子量: 204.269
• InChiKey: IMQUAHFIEUBGDJ-QWHCGFSZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(hydroxy-phenyl-methyl)-2-methyl-cyclopentanone 在 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以58%的产率得到(+)-2-benzoyl-2-methylcyclopentanone
  参考文献：
  名称：

  Construction of quaternary carbon centers by a base-catalyzed enantioselective aldol reaction and related reactions of trimethoxysilyl enol ethers

  摘要：

  The aldol reactions of trimethoxysilyl enol ethers catalyzed by lithium binaphtholate were found to be powerful tools for the construction of quaternary asymmetric carbon centers. The stereoselectivities were greatly affected by the presence of water. Trimethoxysilyl enol ether derived from a cyclic ketone, such as cyclohexanone, was used as a substrate to obtain the anti-adduct preferentially under anhydrous conditions; by contrast, the syn-adduct was preferentially obtained under aqueous conditions with high stereoselectivity. The aldol-Tishchenko reaction of a trimethoxysilyl enol ether derived from acyclic ketones proceeded to give monoacyl 1,3-diol derivatives in high enantioselectivities. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2012.03.096
• 作为产物：
  描述：

  甲基环戊烯醇酮 在 hydrido(phosphonite)cobalt(I) 作用下， 以 四氢呋喃 为溶剂， 反应 17.5h， 生成 2-(hydroxy-phenyl-methyl)-2-methyl-cyclopentanone
  参考文献：
  名称：

  光控钴催化 α,β-不饱和酮的选择性硼氢化

  摘要：

  摘要亲核试剂与 α,β-不饱和羰基化合物的 1,2 和 1,4 加成之间的选择性通常通过向底物或试剂中添加化学计量添加剂来改变，以增加其“硬”或“软”特性。在这里，我们展示了一种概念上不同的方法，该方法依赖于用可见光控制催化剂的配位范围。通过这种方式，我们使反应偏向两条不同的途径，从而在 α,β-不饱和酮的催化硼氢化中产生对比产物。这包括通过 1,4-选择性硼氢化反应直接获得以前难以捉摸的环状烯醇硼酸盐，为一锅法获得稀有的顺醇醛产品提供了一种直接且立体选择性的途径。DFT 计算和机械实验证实了两种不同的机制是有效的，支撑着这种不寻常的光控选择性开关。

  DOI：

  10.1002/ange.202009893

文献信息

• Unusual Highly Regioselective Direct Aldol Additions with a Moisture-Resistant and Highly Efficient Titanium Catalyst
  作者：Rainer Mahrwald、Bernd Schetter

  DOI：10.1021/ol052637z

  日期：2006.1.1

  [reaction: see text] The extremely robust and water-stable tetranuclear complex Ti(4)(mu-BINOLato)(6)(mu(3)-OH)(4) was found to catalyze the direct aldol addition with high regioselectivities at the more steric alpha-encumbered side of unsymmetrical ketones. As few as 0.2 mol % loadings with this cluster were enough to afford complete conversions. The reaction proceeds very smoothly without a significant

  [反应：见正文]发现极其坚固且水稳定的四核复合物Ti（4）（mu-BINOLato）（6）（mu（3）-OH）（4）催化高羟选择性的直接羟醛加成反应。不对称酮的立体位偏侧。该簇的低至0.2 mol％的负载量足以提供完整的转化率。反应进行得非常顺利，没有大量的副产物。描述了四元立体中心的形成。
• Toru, Takeshi; Wakayama, Toshiyuki; Watanabe, Yoshihiko, Phosphorus, Sulfur and Silicon and the Related Elements, 1992, vol. 67, # 1-4, p. 253 - 256
  作者：Toru, Takeshi、Wakayama, Toshiyuki、Watanabe, Yoshihiko、Ueno, Yoshio

  DOI：——

  日期：——
• Photocontrolled Cobalt Catalysis for Selective Hydroboration of α,β‐Unsaturated Ketones
  作者：Frédéric Beltran、Enrico Bergamaschi、Ignacio Funes‐Ardoiz、Christopher J. Teskey

  DOI：10.1002/ange.202009893

  日期：2020.11.16

  In this way, we bias the reaction down two divergent pathways, giving contrasting products in the catalytic hydroboration of α,β‐unsaturated ketones. This includes direct access to previously elusive cyclic enolborates, via 1,4‐selective hydroboration, providing a straightforward and stereoselective route to rare syn‐aldol products in one‐pot. DFT calculations and mechanistic experiments confirm two

  摘要亲核试剂与 α,β-不饱和羰基化合物的 1,2 和 1,4 加成之间的选择性通常通过向底物或试剂中添加化学计量添加剂来改变，以增加其“硬”或“软”特性。在这里，我们展示了一种概念上不同的方法，该方法依赖于用可见光控制催化剂的配位范围。通过这种方式，我们使反应偏向两条不同的途径，从而在 α,β-不饱和酮的催化硼氢化中产生对比产物。这包括通过 1,4-选择性硼氢化反应直接获得以前难以捉摸的环状烯醇硼酸盐，为一锅法获得稀有的顺醇醛产品提供了一种直接且立体选择性的途径。DFT 计算和机械实验证实了两种不同的机制是有效的，支撑着这种不寻常的光控选择性开关。
• Construction of quaternary carbon centers by a base-catalyzed enantioselective aldol reaction and related reactions of trimethoxysilyl enol ethers
  作者：Tomonori Ichibakase、Tetsuya Kaneko、Yuya Orito、Shunsuke Kotani、Makoto Nakajima

  DOI：10.1016/j.tet.2012.03.096

  日期：2012.6

  The aldol reactions of trimethoxysilyl enol ethers catalyzed by lithium binaphtholate were found to be powerful tools for the construction of quaternary asymmetric carbon centers. The stereoselectivities were greatly affected by the presence of water. Trimethoxysilyl enol ether derived from a cyclic ketone, such as cyclohexanone, was used as a substrate to obtain the anti-adduct preferentially under anhydrous conditions; by contrast, the syn-adduct was preferentially obtained under aqueous conditions with high stereoselectivity. The aldol-Tishchenko reaction of a trimethoxysilyl enol ether derived from acyclic ketones proceeded to give monoacyl 1,3-diol derivatives in high enantioselectivities. (C) 2012 Elsevier Ltd. All rights reserved.