threo-3-hydroxy-2,4,4-trimethyl-1-phenyl-1-pentanone

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: threo-3-hydroxy-2,4,4-trimethyl-1-phenyl-1-pentanone
• 英文别名: 3-hydroxy-2,4,4-trimethyl-1-phenylpentan-1-one；3-hydroxy-2,4,4-trimethyl-1-phenyl-pentanone；(S)-alpha-[(S)-1-Hydroxy-2,2-dimethylpropyl]propiophenone；(2S,3S)-3-hydroxy-2,4,4-trimethyl-1-phenylpentan-1-one
• 化学式: C₁₄H₂₀O₂
• 分子量: 220.312
• InChiKey: BATLYISGCNQVRP-MFKMUULPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  特戊醛 、 2-溴苯丙酮 在 四氯化钛 、 三(邻甲基苯基)磷 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以100%的产率得到threo-3-hydroxy-2,4,4-trimethyl-1-phenyl-1-pentanone
  参考文献：
  名称：

  Phosphine/Lewis Acid Mediated Reformatsky-type Reaction of α-Bromoketone or -Thioester Derivatives

  摘要：

  (邻甲苯基)3P/TiCl4 的组合有效地促进了 α-溴酮或硫代酯衍生物与各种醛的 Reformatsky 型反应，并以良好的收率和高非对映选择性获得了相应的 β-羟基羰基化合物。

  DOI：

  10.1246/cl.2002.126

文献信息

• Gallium(III) Triflate Catalyzed Diastereoselective Mukaiyama Aldol Reaction by Using Low Catalyst Loadings
  作者：Baptiste Plancq、Lyse Carole Justafort、Mathieu Lafantaisie、Thierry Ollevier

  DOI：10.1002/ejoc.201301100

  日期：2013.10

  A mild method for the diastereoselective Mukaiyama aldol reaction is reported. By using a low loading of the gallium(III) triflate catalyst (down to 0.01 mol-%), the transformation proceeds efficiently to afford the corresponding β-hydroxy ketones in yields up to 92 %. To the best of our knowledge, this is the first report of a metal triflate acting as a safe, bench-stable, and slow-releasing source

  报道了非对映选择性 Mukaiyama 醛醇反应的温和方法。通过使用低负载量的三氟甲磺酸镓 (III) 催化剂（低至 0.01 mol-%），转化有效地进行，以高达 92% 的产率提供相应的 β-羟基酮。据我们所知，这是首次报道金属三氟甲磺酸盐可作为安全、长期稳定且缓慢释放的三氟甲磺酸来源，用于向山羟醛反应。
• Development of Asymmetric Reactions Catalyzed by Chiral Organotin-Alkoxide Reagents
  作者：Akira Yanagisawa、Kazuhiro Yoshida

  DOI：10.1002/tcr.201200019

  日期：2013.2

  of an alcohol. In this Personal Account, we describe three types of asymmetric transformation that proceed through a chiral tin enolate: 1) The asymmetric aldol reaction of alkenyl esters or unsaturated lactones with aldehydes or isatins; 2) the asymmetric three-component Mannich-type reaction of alkenyl esters and related cycloaddition reactions; and 3) the asymmetric N-nitroso aldol reaction of unsaturated

  在几乎中性的反应条件下进行不对称催化是光学活性极性分子有效合成的关键。我们开发了一种无环或环状烯基酯的催化对映选择性反应，方法是使用（S）-BINOL衍生的手性二溴化锡试剂，该试剂在3或3'位具有庞大的芳基作为手性预催化剂，醇钠和醇，其中在其中原位产生手性醇锡溴化物，并在醇的帮助下再循环。在此个人帐户中，我们描述了通过手性锡烯酸酯进行的三种类型的不对称转化：1）烯基酯或不饱和内酯与醛或靛红的不对称醛醇缩合反应；2）烯基酯的不对称三组分曼尼希型反应及相关的环加成反应；3）不饱和内酯与亚硝基芳烃的不对称N-亚硝基醛醇缩合反应。
• Methanol-Assisted Catalysis by Chiral Tin Methoxides: An Alternative Asymmetric Aldol Process
  作者：Akira Yanagisawa、Tomoya Satou、Atsuto Izumiseki、Youichi Tanaka、Masahiko Miyagi、Takayoshi Arai、Kazuhiro Yoshida

  DOI：10.1002/chem.200901822

  日期：2009.11.2

  Opening a tin of catalysts: A catalytic enantioselective aldol reaction of alkenyl trichloroacetates with aldehydes was achieved using a (S)‐BINOL‐derived chiral organotin(IV) dibromide possessing a 4‐tert‐butylphenyl group at the 3‐ and 3′‐position as a chiral pre‐catalyst in the presence of sodium methoxide and methanol (see scheme).

  打开催化剂罐头：使用（S）-BINOL衍生的手性有机锡（IV）二溴化物在3和3'位置具有4-叔丁基苯基，实现了三氯乙酸烯基酯与醛的催化对映选择性醛醇缩合反应在甲醇钠和甲醇存在下用作手性预催化剂（参见方案）。
• Reexamination of CeCl₃ and InCl₃ as Activators in the Diastereoselective Mukaiyama Aldol Reaction in Aqueous Media
  作者：Omar Muñoz-Muñiz、Martina Quintanar-Audelo、Eusebio Juaristi

  DOI：10.1021/jo026713c

  日期：2003.2.1

  A search for suitable reaction conditions in Mukaiyama-type aldol condensations activated by CeCl3 and InCl3 revealed that the reaction proceeds best in i-PrOH/H2O (95:5). Contrary to literature precedent, no reaction was observed in pure water, and the encountered destruction of the starting silyl enol ether can be ascribed to initial hydrolysis of the Lewis acid. As anticipated from the dual parameter (pK(h), WERC value) characteristics of CeCl3 and InCl3, the former proved more efficient as Lewis acid-promoter, in terms of reaction speed and yield. Nevertheless, InCl3 was a superior catalyst during evaluation of the diastereoselectivity of the process. In this regard, determination of diastereoselectivity as a function of time showed that the InCl3-catalyzed reaction is irreversible, whereas the CeCl3-catalyzed reaction is a reversible process. In both cases, formation of the syn product is kinetically preferred, although DeltaDeltaG(273K)(double dagger)(InCl3) = 1.50 kcal/mol versus DeltaDeltaG(273K)(double dagger)(CeCl3) = 0.38 kcal/mol. Molecular modeling (semiempirical PM3, ab initio HF/3-21G*, hybrid B3LYP/321G*, and B3LYP/LANL2DZ) of the diastereoselective aldol reaction promoted by InCl3 supports a "closed", Zimmermann-Traxler transition state.