(2R,4S)-4-o-Tolyloxy-pentan-2-ol | 322478-47-7

• 英文名称: (2R,4S)-4-o-Tolyloxy-pentan-2-ol
• CAS: 322478-47-7
• 化学式: C₁₂H₁₈O₂
• 分子量: 194.274
• InChiKey: PQMSZWGZOJRLQB-MNOVXSKESA-N

物化性质

• 沸点：
  286.3±15.0 °C(Predicted)
• 密度：
  1.001±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.53
• 重原子数：
  14.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  29.46
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (2R,4S)-4-o-Tolyloxy-pentan-2-ol 在 偶氮二甲酸二异丙酯 、 三乙胺 、 三苯基膦 、 苯甲酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 12.0h， 生成
  参考文献：
  名称：

  Remote stereocontrol of intramolecular rhodium carbene addition driven by a small and flexible chiral 2,4-pentanediol tether

  摘要：

  Intramolecular rhodium carbenoid additions were studied using 2,4-pentanidiol as a chiral tether between a diazo group, a precursor of the carbene, and an aromatic group to be reacted with the carbene. The reaction was designed to perform the addition at a remote position, conserving the original high stereoselectivity appeared at additions near the tether, in addition to high regioselectivity and sufficient reaction efficiency. Substitution on the near reaction sites, the carbene carbon and aromatic group, in the reactant was effective to relegate the reaction site to a remote position. In the present study, two remote reactions, one dealing with C-H insertion and the other classified in Buchner reaction, were found to give sole products in high yields. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2012.03.009
• 作为产物：
  描述：

  (2R,4R)-pentanediol 、 邻甲酚 在 偶氮二甲酸二异丙酯 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 反应 96.0h， 生成 (2R,4S)-4-o-Tolyloxy-pentan-2-ol
  参考文献：
  名称：

  Remote stereocontrol of intramolecular rhodium carbene addition driven by a small and flexible chiral 2,4-pentanediol tether

  摘要：

  Intramolecular rhodium carbenoid additions were studied using 2,4-pentanidiol as a chiral tether between a diazo group, a precursor of the carbene, and an aromatic group to be reacted with the carbene. The reaction was designed to perform the addition at a remote position, conserving the original high stereoselectivity appeared at additions near the tether, in addition to high regioselectivity and sufficient reaction efficiency. Substitution on the near reaction sites, the carbene carbon and aromatic group, in the reactant was effective to relegate the reaction site to a remote position. In the present study, two remote reactions, one dealing with C-H insertion and the other classified in Buchner reaction, were found to give sole products in high yields. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2012.03.009

文献信息

• Asymmetric meta-arene–alkene photocycloaddition controlled by a 2,4-pentanediol tether
  作者：Kazutake Hagiya、Akiko Yamasaki、Tadashi Okuyama、Takashi Sugimura

  DOI：10.1016/j.tetasy.2004.03.017

  日期：2004.5

  Photo-irradiation of a substrate having phenyl and vinyl groups resulted in a stereocontrolled meta-arene-alkene cycloaddition when the two groups were connected by a chiral 2,4-pentanediol tether. The regioselectivity during the ring closing step after the initial addition was dependent on the stereochemistry of the tether and the photolysis conditions. The substrate bearing a p-tolyl or 3,5-xylyl group instead of the phenyl also underwent strict stereocontrolled addition. In the case of the o- and m-tolyl substrates, the regioselectivity due to the unsymmetric substitution of the arene moiety was also fully controlled. (C) 2004 Elsevier Ltd. All rights reserved.
• Entropy-Controlled Asymmetric Synthesis. How Differential Activation Entropy Is Induced in Chiral Tethered Reactions
  作者：Takashi Sugimura、Kazutake Hagiya、Yasuhiro Sato、Takahiro Tei、Akira Tai、Tadashi Okuyama

  DOI：10.1021/ol006741m

  日期：2001.1.1

  [GRAPHICS]Kinetic measurements to determine effective molarities of intramolecular reactions using 2,4-pentanediol and related tethers showed that methyl groups on the tether accelerate the major diastereomeric process but decelerate the minor process. The efficient promotion of stereocontrol is suggested to be due to chiral perturbation of the reaction rate through the entropy term, The conformation of the encounter complex of the reagent and reactant moieties was deduced by stereochemical analysis of the intramolecular adducts.