(R)-4-hydroxy-4-(pentafluorophenyl)-butan-2-one

• 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: (R)-4-hydroxy-4-(pentafluorophenyl)-butan-2-one
• 英文别名: (R)-4-hydroxy-4-(pentafluorophenyl)-2-butanone；4-hydroxy-4-(perfluorophenyl)butan-2-one；(4R)-4-hydroxy-4-(2,3,4,5,6-pentafluorophenyl)butan-2-one
• 化学式: C₁₀H₇F₅O₂
• 分子量: 254.156
• InChiKey: JPXWGSXVMCOYSF-SCSAIBSYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (R)-4-hydroxy-4-(pentafluorophenyl)-butan-2-one 、 4-溴异氰酸苯酯 以 氯仿 为溶剂， 反应 120.0h， 以95%的产率得到O-[(R)-1-(pentafluorophenyl)-3-oxobutyl] N-(4-bromophenyl)carbamate
  参考文献：
  名称：

  Cyclic carbonates as sustainable solvents for proline-catalysed aldol reactions

  摘要：

  Ethylene and propylene carbonates, which can be prepared from epoxides and carbon dioxide, are effective solvents for the proline-catalysed, 100% atom economical, asymmetric aldol reaction between enolisable and non-enolisable carbonyl compounds. The optimal cyclic carbonate to use for a particular aldol reaction along with the need for water as a cosolvent appear to be determined by the polarities of the various components present in the reaction mixture. Both cyclic and acyclic ketones can be used as the enamine precursor and react best with electron-deficient aldehydes, such as 4-nitrobenzaldehyde and pentafluorobenzaldehyde. Chemical yields of up to 99%, diastereoselectivities of up to 100% and enantioselectivities of up to 99% can be obtained. The relative and/or absolute configuration of three of the aldol products are determined unambiguously by X-ray diffraction. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2010.03.051
• 作为产物：
  描述：

  五氟苯甲醛 、 丙酮 在 L-脯氨酸 作用下， 以 碳酸乙烯酯 为溶剂， 反应 24.0h， 以99%的产率得到(R)-4-hydroxy-4-(pentafluorophenyl)-butan-2-one
  参考文献：
  名称：

  Cyclic carbonates as sustainable solvents for proline-catalysed aldol reactions

  摘要：

  Ethylene and propylene carbonates, which can be prepared from epoxides and carbon dioxide, are effective solvents for the proline-catalysed, 100% atom economical, asymmetric aldol reaction between enolisable and non-enolisable carbonyl compounds. The optimal cyclic carbonate to use for a particular aldol reaction along with the need for water as a cosolvent appear to be determined by the polarities of the various components present in the reaction mixture. Both cyclic and acyclic ketones can be used as the enamine precursor and react best with electron-deficient aldehydes, such as 4-nitrobenzaldehyde and pentafluorobenzaldehyde. Chemical yields of up to 99%, diastereoselectivities of up to 100% and enantioselectivities of up to 99% can be obtained. The relative and/or absolute configuration of three of the aldol products are determined unambiguously by X-ray diffraction. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2010.03.051

文献信息

• Bisprolinediamides with the Binaphthyl Backbone as Organocatalysts for the Direct Asymmetric Aldol Reaction
  作者：Dorota Gryko、Bartomiej Kowalczyk、Łukasz Zawadzki

  DOI：10.1055/s-2006-939701

  日期：——

  diamines including l,l'-binaphthyl-2,2'-diamine, were prepared in good yields. They were evaluated as catalysts for the direct asymmetric aldol reaction. The presence of the binaphthyl and proline moieties in one molecule has beneficial effects on the stereochemical outcome of the reaction of acetone with a model aldehyde. Furthermore, it was shown that dioxane as the solvent significantly improved both

  以良好的收率制备了一系列衍生自各种芳族二胺（包括 l,l'-binaphthyl-2,2'-diamine）的 L-脯氨酸酰胺。它们被评估为直接不对称醛醇反应的催化剂。一个分子中联萘和脯氨酸部分的存在对丙酮与模型醛反应的立体化学结果具有有益影响。此外，表明二恶烷作为溶剂显着提高了产率和对映选择性，分别达到 89% 和 86%。
• Unexpected Beneficial Effect of ortho-Substituents on the (S)-Proline-Catalyzed Asymmetric Aldol Reaction of Acetone with Aromatic Aldehydes
  作者：Benjamin List、Alberto Martínez、Manuel van Gemmeren

  DOI：10.1055/s-0033-1340920

  日期：——

  An intriguing effect of electronegative 2,6-substituents on the stereochemical outcome of (S) -proline-catalyzed aldol reactions between benzaldehyde derivatives and acetone is reported. Remarkably high enantioselectivities can be achieved with such substrates.

  据报道，带负电的 2,6-取代基对 (S)-脯氨酸催化的苯甲醛衍生物和丙酮之间的羟醛反应的立体化学结果产生了有趣的影响。使用此类底物可以实现非常高的对映选择性。
• Asymmetric Direct Aldol Reaction Catalysed byL-Prolinethioamides
  作者：Dorota Gryko、Radosław Lipiński

  DOI：10.1002/ejoc.200600219

  日期：2006.9

  L-Prolinethioamides have been found to be active catalysts for direct aldol reactions of acetone with aromatic aldehydes, affording aldol products in good yields and with good enantioselectivities. They were prepared from L-proline and simple aliphatic and aromatic amines in optically pure form and in good overall yields. Studies employing ten catalysts allowed us to unequivocally establish the basic

  已发现 L-脯氨酸硫代酰胺是丙酮与芳香醛直接醛醇反应的活性催化剂，以良好的收率和良好的对映选择性提供醛醇产物。它们是由 L-脯氨酸和简单的脂肪族和芳香族胺以光学纯形式制备的，总产率良好。使用十种催化剂的研究使我们能够明确地建立控制 L-脯氨酸硫代酰胺催化的羟醛反应结果的基本原则。特别是，由 L-脯氨酸和 (S)-苯乙胺制备的催化剂以 57% 的产率和 93% 的 ee（在 –78 °C 时为 100% ee）催化了丙酮与 4-氰基苯甲醛的反应。最重要的是，我们发现催化剂与供体或受体之间的空间相互作用对于醛醇加成的立体选择性至关重要，而不需要的咪唑烷硫酮（来自催化剂和丙酮或醛）的形成会降低 ee 和产率。研究了胺部分 (-CSNHR)、不同溶剂和温度的影响，我们还发现催化剂的光学纯度与羟醛产物的 ee 之间存在线性相关性，这支持了反应的假设通过烯胺-亚胺机制进行，仅涉及一分子处于过渡态的催化剂。首次详细研究了1
• L-Prolinethioamides - Efficient Organocatalysts for the Direct Asymmetric Aldol Reaction
  作者：Dorota Gryko、Radosław Lipiński

  DOI：10.1002/adsc.200505247

  日期：2005.12

  been synthesised. They have been evaluated as organocatalysts in the direct asymmetric aldol reaction for the first time. Thioamides exhibit catalytic ability higher than proline itself and the model aldol reaction of 4-cyanobenzaldehyde with acetone proceeds well in the presence of 5 mol % of catalyst (ee up to 100%). Other aromatic aldehydes gave aldol products with high ees and moderate yields. Small

  已经合成了一系列新颖的L-脯氨酸衍生的硫代酰胺。首次在直接不对称醛醇缩合反应中将它们评估为有机催化剂。硫酰胺显示出比​​脯氨酸本身更高的催化能力，并且4-氰基苯甲醛与丙酮的模型醛醇缩合反应在存在5 mol％催化剂（ee最高为100％）的情况下进行得很好。其他芳香醛使醛醇产品具有较高的ee和中等的收率。催化剂结构的细微变化[例如，N -Bn与N -CH（CH 3）以及酸的添加对其活性有深远的影响。观察到催化剂衍生的环状加合物的意外形成，并且建立了它们的反应性，从而提供了对反应过程的有价值的见解。
• Bioinspired Catalysis: Self-Assembly of a Protein and DNA as a Catalyst for the Aldol Reaction in Aqueous Media
  作者：Guangxun Li、Zhuo Tang、Hongxin Liu、Ying-wei Wang、Shiqi Zhang

  DOI：10.1055/s-0036-1591854

  日期：2018.3

  electrostatic interaction in situ proved to be efficient in catalyzing aldol reactions under mild conditions in water. By using a self-assembling catalytic system formed from protamine and DNA, aldol adducts were obtained with high yields and moderate enantioselectivities. Preliminary experiments demonstrated that the chirality of the DNA could be effectively transferred to the reaction product through

  一种有趣的仿生催化剂由容易获得的 DNA 和蛋白质通过原位静电相互作用形成，被证明在水中温和条件下可有效催化羟醛反应。通过使用由鱼精蛋白和 DNA 形成的自组装催化系统，以高产率和中等对映选择性获得了羟醛加合物。初步实验表明，DNA 的手性可以通过结合的分子或蛋白质有效地转移到反应产物上。