(S)-tetrahydro-3,3-diphenyl-1-(2,4,6-trifluorophenyl)-1H,3H-pyrrolo[1,2-c][1,3,2]oxazaborole | 1260503-82-9

• 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: (S)-tetrahydro-3,3-diphenyl-1-(2,4,6-trifluorophenyl)-1H,3H-pyrrolo[1,2-c][1,3,2]oxazaborole
• 英文别名: (S)-Ph2(C5H7BNO)(2,4,6-F3-C6H2)；(3aS)-3,3-diphenyl-1-(2,4,6-trifluorophenyl)-3a,4,5,6-tetrahydropyrrolo[1,2-c][1,3,2]oxazaborole
• CAS: 1260503-82-9
• 化学式: C₂₃H₁₉BF₃NO
• 分子量: 393.216
• InChiKey: FMUCNUHSFGCZEY-NRFANRHFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.24
• 重原子数：
  29
• 可旋转键数：
  3
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (S)-tetrahydro-3,3-diphenyl-1-(2,4,6-trifluorophenyl)-1H,3H-pyrrolo[1,2-c][1,3,2]oxazaborole 在 dimethyl sulfide borane 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 生成 C₂₃H₂₂B₂F₃NO
  参考文献：
  名称：

  Rational electronic tuning of CBS catalyst for highly enantioselective borane reduction of trifluoroacetophenone

  摘要：

  α,α,α-三氟乙酰苯（2），该物质易受BH3非催化还原，可通过使用电子调谐CBS催化剂（1）与BH3反应，将其还原为手性醇，最高可达90%的ee值。通过DFT方法计算，其对映选择性与1–BH3加合物和2之间的轨道能量差异高度相关。

  DOI：

  10.1039/c0cc03706k
• 作为产物：
  描述：

  (S)-(+)-alpha,alpha-二苯基脯氨醇 、 2,4,6-三氟苯硼酸 以 甲苯 为溶剂， 反应 4.0h， 生成 (S)-tetrahydro-3,3-diphenyl-1-(2,4,6-trifluorophenyl)-1H,3H-pyrrolo[1,2-c][1,3,2]oxazaborole
  参考文献：
  名称：

  Rational electronic tuning of CBS catalyst for highly enantioselective borane reduction of trifluoroacetophenone

  摘要：

  α,α,α-三氟乙酰苯（2），该物质易受BH3非催化还原，可通过使用电子调谐CBS催化剂（1）与BH3反应，将其还原为手性醇，最高可达90%的ee值。通过DFT方法计算，其对映选择性与1–BH3加合物和2之间的轨道能量差异高度相关。

  DOI：

  10.1039/c0cc03706k
• 作为试剂：
  描述：

  4'-溴-2,2,2-三氟苯乙酮 在 dimethyl sulfide borane 、 (S)-tetrahydro-3,3-diphenyl-1-(2,4,6-trifluorophenyl)-1H,3H-pyrrolo[1,2-c][1,3,2]oxazaborole 作用下， 以 四氢呋喃 为溶剂， 生成 (S)-1-(4-溴苯基)-2,2,2-三氟乙醇
  参考文献：
  名称：

  Enantioselectivity, swelling and stability of 4-hydroxyprolinol containing acrylic polymer beads in the asymmetric reduction of ketones

  摘要：

  A new 4-hydroxy-alpha,alpha-diphenyl-L-prolinol containing polymethacrylate, prepared without chromatography by a large scale adaptable synthesis, has been evaluated as a catalyst in the asymmetric reduction of 1-arylethanones. Using 1-(4-bromophenyl)ethanone as the model substance, the reduction was tested with various borane sources and solvents. The best swellings of the polymer and reactivity were observed in THF using N,N-diethylaniline borane complex as the hydride source. The selectivity in the reduction of 1-(4-bromophenyl)ethanone was found to depend on the substrate concentration and catalyst loading. Using the best conditions identified, a series of 1-arylethanones was reduced to their corresponding enantioenriched secondary alcohols. High rates and ee-values were obtained in the reduction of acetophenones containing electron withdrawing groups in the aromatic ring, whereas a moderate selectivity was the result for products containing electron donating aromatic substituents. Upon recovery of the polymer beads, it was found that vacuum drying led to extensive rupturing, while the bead structure was intact if washed with methanol and air dried at atmospheric pressure. Repeated use of the polymer catalyst gave the product alcohol with a lower 90% ee. Elemental analysis showed this to be due to the loss of the chiral prolinol unit. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2011.12.001

文献信息

• Rational electronic tuning of CBS catalyst for highly enantioselective borane reduction of trifluoroacetophenone
  作者：Toshinobu Korenaga、Kenji Nomura、Kazutaka Onoue、Takashi Sakai

  DOI：10.1039/c0cc03706k

  日期：——

  α,α,α-Trifluoroacetophenone (2), which is susceptible to noncatalytic reduction by BH3, could be reduced to chiral alcohol up to 90% ee by using electronically tuned-CBS catalyst (1) with BH3. The enantioselectivities highly correlated with the differential orbital energies between 1–BH3 adduct and 2, which were calculated by DFT method.

  α,α,α-三氟乙酰苯（2），该物质易受BH3非催化还原，可通过使用电子调谐CBS催化剂（1）与BH3反应，将其还原为手性醇，最高可达90%的ee值。通过DFT方法计算，其对映选择性与1–BH3加合物和2之间的轨道能量差异高度相关。