threo-1-hydroxy-2,5-dimethyl-1-phenyl-3-hexanone | 71908-04-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: threo-1-hydroxy-2,5-dimethyl-1-phenyl-3-hexanone
• 英文别名: (1R,2S)-1-hydroxy-2,5-dimethyl-1-phenylhexan-3-one
• CAS: 71908-04-8；71908-05-9
• 化学式: C₁₄H₂₀O₂
• 分子量: 220.312
• InChiKey: OISWSIJYMOOQFZ-BXUZGUMPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  16
• 可旋转键数：
  5
• 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：

  4-甲基-2-戊酮 在 (R,R)-cobalt(II) 四氢糠醇 、 sodium tetrahydroborate 、 乙醇 作用下， 以 氯仿 为溶剂， 反应 10.0h， 生成 threo-1-hydroxy-2,5-dimethyl-1-phenyl-3-hexanone
  参考文献：
  名称：

  旋光性钴配合物催化对映选择性硼氢化物的还原。

  摘要：

  在催化量的光学活性钴（II）络合物催化剂的存在下，芳香族酮或亚胺对映体的高度对映选择性硼氢化物还原。该对映选择性还原是使用精确预改性的硼氢化物与醇（例如四氢糠醇，乙醇和甲醇）进行的。通过选择合适的醇作为改性剂和合适的催化剂β-酮亚氨基配体，可以获得高的光学收率。对映选择性硼氢化物还原已成功应用于光学活性的1,3-二醇的制备，双酰基二茂铁的立体选择性还原以及1,3-二羰基化合物的动态和/或动力学拆分。

  DOI：

  10.1002/chem.200304794

文献信息

• Stereoselective aldol condensations via boron enolates
  作者：D. A. Evans、J. V. Nelson、E. Vogel、T. R. Taber

  DOI：10.1021/ja00401a031

  日期：1981.6

  carboxylic acid derivatives with dialkylboryl triflates in the presence of a tertiary amine and the subsequent aldol condensations of these boron enolates was conducted. The stereochemistry of the enolates formed from acyclic ketones was found to be dependent on the structure of the ketone, the dialkylboryl triflate, and the tertiary amine. A mechanism for the enolization involving initial coordination of

  在叔胺的存在下，对各种酮和羧酸衍生物与二烷基硼基三氟甲磺酸酯的烯醇化以及这些硼烯醇化物的随后羟醛缩合进行了详细研究。发现由无环酮形成的烯醇化物的立体化学取决于酮、二烷基硼基三氟甲磺酸酯和叔胺的结构。提出了一种涉及硼基三氟甲磺酸酯与酮羰基的初始配位以及随后由胺去质子化的烯醇化机制来解释结果。衍生自这些无环酮的硼烯醇化物以良好的收率与许多醛进行羟醛缩合。无论酮或硼配体的结构如何，在这些无环酮的烯醇几何结构和产物羟醛立体化学之间观察到始终良好的相关性。然而，对于衍生自环己酮的硼烯醇化物，羟醛立体选择性取决于硼配体和溶剂。在这种情况下，在四氢呋喃中使用环戊基己基硼烯醇化物作为溶剂导致缩合中的完全立体控制。虽然简单的酯和酰胺不能用三氟甲磺酸酯试剂进行烯醇化，但硫代丙酸叔丁酯很容易转化为反式烯醇酯。该烯醇化物的羟醛缩合的立体选择性也取决于硼配体和溶剂；同样，这些参数的正确选择允许对冷凝进行全面的立体控
• Highly Chemo-, Diastereo-, and Enantioselective Reduction of 1,2-Dialkyl-3-aryl-1,3-diketones for Preparation of Aldol-Type Compounds
  作者：Yuhki Ohtsuka、Kiichirou Koyasu、Daichi Miyazaki、Taketo Ikeno、Tohru Yamada

  DOI：10.1021/ol016676w

  日期：2001.10.1

  [GRAPHICS]Highly chemo-, diastereo-, and enantioselective borohydride reduction of 2-substituted-1,3-diketones was achieved in the presence of the optically active beta -ketoiminato cobalt complex catalysts to afford the optically active 2-substituted-3-hydroxyketones. The present catalytic and enantioselective reduction could provide an alternative potential for preparation of optically active ant aldol-type compounds.
• Enolboration. 5. An examination of the effects of amine, solvent, and other reaction parameters on the stereoselective enolboration of ketones with various Chx2BX reagents. An optimized procedure to achieve the stereoselective synthesis of E enol borinates from representative ketones using Chx2BCl/Et3N
  作者：Kumaraperumal Ganesan、Herbert C. Brown

  DOI：10.1021/jo00077a046

  日期：1993.12

  The effects of amine, solvent, concentration, temperature and other reaction parameters in controlling the enolate geometry have been systematically investigated in the present study. A B-11 NMR study of the interaction of representative tertiary amines of variable steric requirements with dicyclohexylchloroborane, ChX2BCl, suggests that the smaller amines coordinate strongly with Chx2BCl, while the more bulky amines do not. These amines have also been examined for the enolboration of diethyl ketone with ChX2BCI, in order to understand the effect of the steric requirements of the amine on the enolate geometry. While the smaller amines favor formation of E enol borinate, the more hindered amines favor formation of the isomeric Z enol borinate. Triethylamine and N,N-diisopropylethylamine, the best amines selected in terms of yield and selectivity, have also been compared for the enolboration of two model ketones, diethyl ketone and propiophenone, using various Chx2BX reagents (X = Cl, Br, I, OMs, and OTf) to understand their effect with different ketones and reagents. Detailed studies for the enolboration of diethyl ketone with ChX2BCI/Et3N, with the hope of understanding the various effects on the enolate geometry and of improving the E enolate selectivity, suggest that formation of the E enolates are highly favored in nonpolar solvents and in dilute medium, whereas the corresponding Z enolates are more favored in polar solvents and in relatively concentrated medium. The other reaction parameters, such as the enolization and the aldolization temperatures, and the order and the rate of addition of the various substrates, have essentially no influence on the stereochemistry. However, the aldolization at -78-degrees-C for 2 h without allowing the reaction mixture to warm to room temperature improves the anti aldol selectivity. An understanding of these various effects in controlling the stereochemistry of the enolboration and the achievement of the selective synthesis of E enol borinates from representative ketones using Chx2-BCl/Et3N under optimized reaction conditions are emphasized in this exploratory study.
• Enantioselective Borohydride Reduction Catalyzed by Optically Active Cobalt Complexes
  作者：Tohru Yamada、Takushi Nagata、Kiyoaki D. Sugi、Kiyotaka Yorozu、Taketo Ikeno、Yuhki Ohtsuka、Daichi Miyazaki、Teruaki Mukaiyama

  DOI：10.1002/chem.200304794

  日期：2003.9.22

  enantioselective borohydride reduction of aromatic ketones or imines to the corresponding alcohols was developed in the presence of a catalytic amount of an optically active cobalt(II) complex catalyst. This enantioselective reduction is carried out using a precisely premodified borohydride with alcohols such as tetrahydrofurfuryl alcohol, ethanol and methanol. High optical yields are obtained by choosing

  在催化量的光学活性钴（II）络合物催化剂的存在下，芳香族酮或亚胺对映体的高度对映选择性硼氢化物还原。该对映选择性还原是使用精确预改性的硼氢化物与醇（例如四氢糠醇，乙醇和甲醇）进行的。通过选择合适的醇作为改性剂和合适的催化剂β-酮亚氨基配体，可以获得高的光学收率。对映选择性硼氢化物还原已成功应用于光学活性的1,3-二醇的制备，双酰基二茂铁的立体选择性还原以及1,3-二羰基化合物的动态和/或动力学拆分。