syn-2-methyl-3-phenyl-3-(perfluorophenyl)-1-propanol

• 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: syn-2-methyl-3-phenyl-3-(perfluorophenyl)-1-propanol
• 英文别名: (2R,3R)-2-methyl-3-(2,3,4,5,6-pentafluorophenyl)-3-phenylpropan-1-ol
• 化学式: C₁₆H₁₃F₅O
• 分子量: 316.271
• InChiKey: YVLXLXFOVCNBRZ-WCBMZHEXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  苯基丙酮 在 chloro(1,5-cyclooctadiene)rhodium(I) dimer 、 三苯基膦 sodium hydroxide 、 双氧水 、 四氯化钛 、 四丁基碘化铵 、 sodium hydride 、 锌 、 儿萘酚硼烷 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 32.5h， 生成 syn-2-methyl-3-phenyl-3-(perfluorophenyl)-1-propanol
  参考文献：
  名称：

  Substrate-controlled diastereoselectivities in catalyzed and uncatalyzed hydroborations of acyclic allylic alcohol derivatives: secondary orbital effects involving d.pi.-p.pi. interactions

  摘要：

  Rhodium-mediated hydroborations of allylic alcohol derivatives 1-9 followed by oxidation give predominantly syn-2-methyl 1,3-diols whereas conventional hydroborations of the same substrates afford mostly anti products. It is proposed that mixing of delta*-orbitals involved in bonding at the asymmetric center with pi*-orbitals of the alkene lowers the LUMO involved in complexation of rhodium, and this could control diastereofacial selectivities in catalyzed hydroborations. Steric effects in catalyzed hydroborations are also discussed. The resulting hypotheses are tested with respect to catalyzed and uncatalyzed hydroborations of phenyl-substituted allylic alcohol derivatives 17-19 and Ph(C6F5)CHCM(e) = CH2 (21) (a model substrate with aromatic groups of a similar size but different electronic properties attached to the chiral center). All experimental observations described here for catalyzed hydroborations of chiral alkenes are consistent with the proposals outlined above.

  DOI：

  10.1021/jo00003a023

文献信息

• Substrate-controlled diastereoselectivities in catalyzed and uncatalyzed hydroborations of acyclic allylic alcohol derivatives: secondary orbital effects involving d.pi.-p.pi. interactions
  作者：Kevin Burgess、Juanita Cassidy、Michael J. Ohlmeyer

  DOI：10.1021/jo00003a023

  日期：1991.2

  Rhodium-mediated hydroborations of allylic alcohol derivatives 1-9 followed by oxidation give predominantly syn-2-methyl 1,3-diols whereas conventional hydroborations of the same substrates afford mostly anti products. It is proposed that mixing of delta*-orbitals involved in bonding at the asymmetric center with pi*-orbitals of the alkene lowers the LUMO involved in complexation of rhodium, and this could control diastereofacial selectivities in catalyzed hydroborations. Steric effects in catalyzed hydroborations are also discussed. The resulting hypotheses are tested with respect to catalyzed and uncatalyzed hydroborations of phenyl-substituted allylic alcohol derivatives 17-19 and Ph(C6F5)CHCM(e) = CH2 (21) (a model substrate with aromatic groups of a similar size but different electronic properties attached to the chiral center). All experimental observations described here for catalyzed hydroborations of chiral alkenes are consistent with the proposals outlined above.