1-[((2S,3S)-3-phenyloxiran-2-yl)methoxy]-2-methoxyethane | 250605-16-4

• 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: 1-[((2S,3S)-3-phenyloxiran-2-yl)methoxy]-2-methoxyethane
• 英文别名: (2S,3S)-2-(2-methoxyethoxymethyl)-3-phenyloxirane
• CAS: 250605-16-4
• 化学式: C₁₂H₁₆O₃
• 分子量: 208.257
• InChiKey: HRWWAMXTFOMBRC-RYUDHWBXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  31
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-[((2S,3S)-3-phenyloxiran-2-yl)methoxy]-2-methoxyethane 在 sodium azide 、 lithium perchlorate 作用下， 以 乙腈 为溶剂， 反应 24.0h， 以1.30 g的产率得到(1R,2R)-1-azido-3-(2-methoxyethoxy)-1-phenylpropan-2-ol
  参考文献：
  名称：

  A New Family of Modular Chiral Ligands for the Catalytic Enantioselective Reduction of Prochiral Ketones

  摘要：

  A family of enantiomerically pure (4R,5R)-2-alkyl-4-phenyl-5-(R-oxymethyl) 1,3,2-oxazaborolidines (5) [boron substituent: H, CH3, n-C4H9; R-oxy group: CH3O, CH3OCH2CH2O, CH3(OCH2CH2)(2)O, PhCH2O, Ph2CHO, Ph3CO] has been prepared from (2S,3S)-2,3-epoxy-3-phenylpropanol (2) through a four-step sequence involving protection of the alcohol, regioselective ring-opening of the epoxide with sodium azide in acetonitrile in the presence of LiClO4, reduction of the azido group (H-2/PdC/MeOH or NaBH4/THF-MeOH), and formation of the oxazaborolidine ring with the appropriate boron reagent. Both the boron substituent and the R-oxy group have been optimized for maximal enantioselectivity in the reduction of prochiral ketones with borane. The optimal oxazaborolidine (5a-Me) [boron substituent: CH3; R-oxy group: CH3O] has been employed (10% molar amount, THF, 0 degrees C to room temperature) in the reduction of a representative family of 10 substrates comprising alkyl aryl ketones and dialkyl ketones. In these reductions, Ba-Rie induces the formation of secondary alcohols of S configuration with high enantioselectivity (93% mean enantiomeric excess). The origin of the enantioselectivity in the reduction has been rationalized by means of semiempirical AM1 calculations.

  DOI：

  10.1021/jo990942q
• 作为产物：
  描述：

  苯基甘油醇 、 2-碘乙基甲醚 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 15.0h， 以79%的产率得到1-[((2S,3S)-3-phenyloxiran-2-yl)methoxy]-2-methoxyethane
  参考文献：
  名称：

  A New Family of Modular Chiral Ligands for the Catalytic Enantioselective Reduction of Prochiral Ketones

  摘要：

  A family of enantiomerically pure (4R,5R)-2-alkyl-4-phenyl-5-(R-oxymethyl) 1,3,2-oxazaborolidines (5) [boron substituent: H, CH3, n-C4H9; R-oxy group: CH3O, CH3OCH2CH2O, CH3(OCH2CH2)(2)O, PhCH2O, Ph2CHO, Ph3CO] has been prepared from (2S,3S)-2,3-epoxy-3-phenylpropanol (2) through a four-step sequence involving protection of the alcohol, regioselective ring-opening of the epoxide with sodium azide in acetonitrile in the presence of LiClO4, reduction of the azido group (H-2/PdC/MeOH or NaBH4/THF-MeOH), and formation of the oxazaborolidine ring with the appropriate boron reagent. Both the boron substituent and the R-oxy group have been optimized for maximal enantioselectivity in the reduction of prochiral ketones with borane. The optimal oxazaborolidine (5a-Me) [boron substituent: CH3; R-oxy group: CH3O] has been employed (10% molar amount, THF, 0 degrees C to room temperature) in the reduction of a representative family of 10 substrates comprising alkyl aryl ketones and dialkyl ketones. In these reductions, Ba-Rie induces the formation of secondary alcohols of S configuration with high enantioselectivity (93% mean enantiomeric excess). The origin of the enantioselectivity in the reduction has been rationalized by means of semiempirical AM1 calculations.

  DOI：

  10.1021/jo990942q

文献信息

• Highly Modular POP Ligands for Asymmetric Hydrogenation: Synthesis, Catalytic Activity, and Mechanism
  作者：Héctor Fernández-Pérez、Steven M. A. Donald、Ian J. Munslow、Jordi Benet-Buchholz、Feliu Maseras、Anton Vidal-Ferran

  DOI：10.1002/chem.200902915

  日期：2010.6.11

  pure POP ligands (phosphine–phosphite), straightforwardly available in two synthetic steps from enantiopure Sharpless epoxy ethers is reported. Both the alkyloxy and phosphite groups can be optimized for maximum enantioselectivity and catalytic activity. Their excellent performance in the Rh‐catalyzed asymmetric hydrogenation of a wide variety of functionalized alkenes (26 examples) and modular design

  据报道，有一个对映体纯的POP配体（膦-亚磷酸酯）库，可通过对映纯的Sharpless环氧醚在两个合成步骤中直接获得。烷氧基和亚磷酸酯基团均可被优化以实现最大的对映选择性和催化活性。它们在Rh催化的各种官能化烯烃的不对称氢化反应中的优异性能（26个实例）和模块化设计使其对于将来的应用具有吸引力。引线催化剂结合有（小号）-BINOL衍生（BINOL = 1,1'-联-2-萘酚）酯组计算研究揭示了该部分具有对我们的P的行为具有双重作用OP配体。一方面，亚磷酸酯的电子性质阻碍了四种可能的歧管中的两种中的底物的结合和反应。另一方面，BINOL的空间效应可以区分其余两个歧管，从而阐明了这些催化剂的高效率。
• A New Family of Modular Chiral Ligands for the Catalytic Enantioselective Reduction of Prochiral Ketones
  作者：Cristina Puigjaner、Anton Vidal-Ferran、Albert Moyano、Miquel A. Pericàs、Antoni Riera

  DOI：10.1021/jo990942q

  日期：1999.10.1

  A family of enantiomerically pure (4R,5R)-2-alkyl-4-phenyl-5-(R-oxymethyl) 1,3,2-oxazaborolidines (5) [boron substituent: H, CH3, n-C4H9; R-oxy group: CH3O, CH3OCH2CH2O, CH3(OCH2CH2)(2)O, PhCH2O, Ph2CHO, Ph3CO] has been prepared from (2S,3S)-2,3-epoxy-3-phenylpropanol (2) through a four-step sequence involving protection of the alcohol, regioselective ring-opening of the epoxide with sodium azide in acetonitrile in the presence of LiClO4, reduction of the azido group (H-2/PdC/MeOH or NaBH4/THF-MeOH), and formation of the oxazaborolidine ring with the appropriate boron reagent. Both the boron substituent and the R-oxy group have been optimized for maximal enantioselectivity in the reduction of prochiral ketones with borane. The optimal oxazaborolidine (5a-Me) [boron substituent: CH3; R-oxy group: CH3O] has been employed (10% molar amount, THF, 0 degrees C to room temperature) in the reduction of a representative family of 10 substrates comprising alkyl aryl ketones and dialkyl ketones. In these reductions, Ba-Rie induces the formation of secondary alcohols of S configuration with high enantioselectivity (93% mean enantiomeric excess). The origin of the enantioselectivity in the reduction has been rationalized by means of semiempirical AM1 calculations.