(2SR,3RS)-3-hydroxy-2-methyl-1,3-diphenylpropan-1-one

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 直链 1,3-二芳基丙烷
• 英文名称: (2SR,3RS)-3-hydroxy-2-methyl-1,3-diphenylpropan-1-one
• 英文别名: 3-hydroxy-2-methyl-1,3-diphenylpropan-1-one；anti-3-hydroxy-2-methyl-1,3-diphenyl-1-propanone；3-hydroxy-2-methyl-1,3-diphenyl-1-propanone；(2S,3R)-3-hydroxy-2-methyl-1,3-diphenylpropan-1-one
• 化学式: C₁₆H₁₆O₂
• 分子量: 240.302
• InChiKey: YJPANUWAQYSUPC-SWLSCSKDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.19
• 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：

  (2SR,3RS)-3-hydroxy-2-methyl-1,3-diphenylpropan-1-one 在 sodium hydroxide 、 双氧水 、 lithium hydride 作用下， 以 四氢呋喃 、 乙醚 、 乙醇 为溶剂， 反应 47.67h， 生成 (1R,2r,3S)-2-methyl-1,3-diphenyl-1,3-propanediol
  参考文献：
  名称：

  The Role of theα-Stereogenic Center in the Control of Stereoselection in the Reduction ofα-Alkyl-β-hydroxy Ketones: A Highly Diastereoselective Protocol for the Synthesis of 1,2-syn-2-Alkyl-1,3-diols

  摘要：

  Accurate investigations on the role played by an alpha-stereogenic center in controlling the reduction of various classes of beta-hydroxy ketones allowed us to set up a general and highly diastereoselective protocol for the synthesis of 2-alkyl-1,3-diols with 1,2-syn relationship. This methodology is based on the conversion of a beta-hydroxy ketone into the corresponding titanium alcoholate that permits us to organize the substrate in a stable and rigid structure, which stereofacially favors attacking hydride ions. The use of THF as solvent makes available a variety of hydride donors that cover a large spectrum of steric demand: the choice of the more appropriate one depends on the conformational stability of the cyclic intermediate. Excellent results are obtained also in the presence of an additional stereogenic center in the beta-position, even if it exerts a concordant or an opposite steric effect with respect to the alpha-substituent.

  DOI：

  10.1002/1521-3765(20000717)6:14<2590::aid-chem2590>3.0.co;2-x
• 作为产物：
  描述：

  2-iodo-1-phenylpropan-1-one 在 2,6-二甲基吡啶 作用下， 以 四氢呋喃 为溶剂， 反应 8.0h， 生成 (2SR,3RS)-3-hydroxy-2-methyl-1,3-diphenylpropan-1-one
  参考文献：
  名称：

  通过由 α-碘酮和 9-BBN-H 生成的硼烯醇化物进行立体选择性交叉羟醛反应

  摘要：

  通过用 9-BBN-H 处理 α-碘酮，原位顺利生成硼烯醇化物，并通过与各种醛在低温下连续反应以高度非对映选择性的方式生成醛醇。

  DOI：

  10.1246/cl.2002.698

文献信息

• Synthetic control leading to chiral compounds
  作者：Teruaki Mukaiyama、Nobuharu Iwasawa、Rodney W. Stevens、Toru Haga

  DOI：10.1016/s0040-4020(01)82423-6

  日期：1984.1

  A highly diastereoselective cross aldol reaction is developed using divalent tin enolates formed from stannous trifluoromethanesulfonate and carbonyl compounds. The reaction is extended to a highly enantioselective cross aldol reaction employing chiral diamines derived from (S)-proline as ligands.

  使用由三氟甲烷磺酸亚锡和羰基化合物形成的二价烯醇锡开发了高度非对映选择性的交叉醇醛缩合反应。使用衍生自（S）-脯氨酸的手性二胺作为配体，将反应扩展至高度对映选择性的交叉羟醛反应。
• Lithium Acetate-Catalyzed Aldol Reaction between Aldehyde and Trimethylsilyl Enolate in Anhydrous or Water-Containing<i>N</i>,<i>N</i>-Dimethylformamide
  作者：Takashi Nakagawa、Hidehiko Fujisawa、Yuzo Nagata、Teruaki Mukaiyama

  DOI：10.1246/bcsj.77.1555

  日期：2004.8

  AcOLi catalyst, the aldol reaction in water-containing DMF was studied in detail. AcOLi and various metal carboxylates behaved as effective Lewis base catalysts in aldol reactions between trimethylsilyl enolate and aldehydes in DMF-H 2 O (50:1) (Tables 6, 7). One of the most characteristic points of the above reaction that took place in water-containing DMF is that the aldehydes having a free amide

  乙酸锂 (AcOLi) 催化的三甲基甲硅烷基烯醇化物和醛之间的醛醇反应在无水 DMF 或吡啶中顺利进行，在弱碱性条件下以良好至高产率提供相应的醛醇（表 1-5）。这种催化羟醛反应也可以通过使用其他金属羧酸盐顺利进行，这些金属羧酸盐通过用碳酸锂 (Li 2 CO 3 ) 处理羧酸很容易原位制备（表 2，方案 5）。为了展示温和易得的AcOLi催化剂的效果，详细研究了含水DMF中的羟醛反应。AcOLi 和各种金属羧酸盐在 DMF-H 2 O (50:1) 中三甲基甲硅烷基烯醇酯和醛之间的羟醛反应中充当有效的路易斯碱催化剂（表 6、7）。在含水DMF中发生的上述反应的最特征点之一是具有游离酰胺和羟基甚至羧基的醛反应平稳并以中等至高产率提供所需的醛醇29-31（表 8，条目 12-15）。由羧酸酯衍生的三甲基甲硅烷基烯醇化物在上述反应中表现得与优异的亲核试剂相似。这是路易斯碱催化醛醇反应的第一个例
• 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。
• Highly Efficient Redox Isomerization of Allylic Alcohols at Ambient Temperature Catalyzed by Novel Ruthenium-Cyclopentadienyl Complexes—New Insight into the Mechanism
  作者：Belén Martín-Matute、Krisztián Bogár、Michaela Edin、F. Betül Kaynak、Jan-E. Bäckvall

  DOI：10.1002/chem.200500490

  日期：2005.10.7

  complexes have been prepared and used for isomerization of allylic alcohols to the corresponding saturated carbonyl compounds. Complexes bearing CO ligands show higher activity than those with PPh3 ligands. The isomerization rate is highly affected by the substituents on the Cp ring. Tetra(phenyl)methyl-substituted catalysts rapidly isomerize allylic alcohols under very mild reaction conditions (ambient

  已经制备了多种钌环戊二烯基（Cp）配合物，并将其用于烯丙基醇异构化为相应的饱和羰基化合物。带有CO配体的配合物显示出比具有PPh3配体的配合物更高的活性。异构化速率受Cp环上的取代基影响很大。四（苯基）甲基取代的催化剂可在非常温和的反应条件下（环境温度）以短的反应时间快速异构化烯丙醇。取代的烯丙醇已经通过使用Ru-Cp络合物被异构化。对[Ru（Ph5Cp）（CO）2H]（14）催化的异构化的研究表明，氢化钌催化的异构化部分与KOtBu活化的卤化钌的催化机理不同。此外，
• Hydrophobic polymer-supported scandium catalyst for carbon–carbon bond-forming reactions in water
  作者：Shinya Iimura、Kei Manabe、Shū Kobayashi

  DOI：10.1016/j.tet.2004.06.083

  日期：2004.8

  that a hydrophobic polymer-supported scandium(III) catalyst prepared from sulfonated polystyrene resin is an effective catalyst for carbon–carbon bond-forming reactions such as Mukaiyama aldol reactions in water. According to studies on loading levels of scandium, hydrophobicity of the catalyst is a key for the efficient catalysis. The scandium catalyst was successfully recovered and reused. Several

  已经发现，由磺化聚苯乙烯树脂制备的疏水聚合物负载的scan（III）催化剂是有效的碳-碳键形成反应的催化剂，例如水中的Mukaiyama醛醇缩合反应。根据对loading载量的研究，催化剂的疏水性是有效催化的关键。catalyst催化剂已成功回收并重新使用。在醛醇缩合反应中，几种酮而不是醛也用作底物。使用the催化剂在水中还会发生一些1,4-加成反应。