(R)-(E)-3-hexen-2-ol | 189456-20-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (R)-(E)-3-hexen-2-ol
• 英文别名: (2R)-hex-3-en-2-ol；(E,2R)-hex-3-en-2-ol
• CAS: 189456-20-0
• 化学式: C₆H₁₂O
• 分子量: 100.161
• InChiKey: SMOVOSVEEFIBSP-BMMSZFGTSA-N

物化性质

• 沸点：
  139.3±8.0 °C(Predicted)
• 密度：
  0.841±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  7
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (R)-(E)-3-hexen-2-ol 在 potassium tetrachloropalladate(II) 盐酸 、 对苯醌 作用下， 生成 (4R)-4-羟基-2-己酮
  参考文献：
  名称：

  Palladium(II)-Catalyzed Exchange and Isomerization Reactions. 17. Exchange of Chiral Allyl Alcohols with Hydroxide, Methoxide, and Phenyl at High [Cl^-]. Stereochemistry of the Wacker Reaction

  摘要：

  At high [Cl-] (> 2.0 M), PdCl42- catalyzes the exchange of chiral allylic alcohols with hydroxy, methoxy, and phenyl to give chiral allyl-substituted olefins. With unsymmetrical olefins, isomerization occurs along with exchange. The hydroxyl exchange occurs in aqueous solution while the other exchanges are carried out in methanol solution. At low [Cl-] (0.1 M) oxidation to the corresponding beta-hydroxy-, methoxy-, and phenyl-substituted carbonyl compounds occurred. The absolute configurations of the oxidation and exchange products should be the same if the same mode of addition to the Pd(II)-pi-complex is operative. The absolute configurations of the oxidation and exchange products for the phenylation reaction were the same, while for hydroxy and methoxy they were different. This result indicates methanol and water must have different stereochemistries of addition at high and low [Cl-]. Thus, previous studies showing anti hydroxypalladation at high [Cl-] are not valid indicators of the stereochemistry at low [Cl-]. If anti addition occurs at high [Cl-], the addition must be syn at low [Cl-].

  DOI：

  10.1021/jo9906274
• 作为产物：
  描述：

  (S,R)-反式-3-己烯-2-醇 生成 (2S)-hex-3-en-2-ol 、 (R)-(E)-3-hexen-2-ol
  参考文献：
  名称：

  气相中的手性离子。1. O-Protonated (S)-trans-4-Hexen-3-ol 的分子内消旋和异构化

  摘要：

  (S)-trans-4-hexen-3-ol (1S) 的酸催化外消旋和区域异构化已在气态 CH4 和 C3H8 中在 720 Torr 和 40-120 °C 温度范围内进行了研究。由激发的 O-质子化 (S)-trans-4-hexen-3-ol (IS) 的单分子断裂产生的游离 1-methyl-3-ethylallyl 阳离子对外消旋化和异构化产物的贡献通过生成它们进行评估来自异构 2,4-己二烯的质子化并通过在相同的实验条件下研究它们对 H218O 的行为。在整个温度范围内，IS 气相外消旋化的速率常数 (1.4-21.3 × 106 s-1) 超过其异构化的速率常数 (1.0-9.9 × 106 s-1)。实验结果，结合模型[C3H5+/H2O]系统的从头算理论计算，

  DOI：

  10.1021/ja960212p

文献信息

• Intracomplex CH₃OH Walking around Optically Active 1-Methyl-3-ethylallyl Cations. A Gas-Phase Kinetic Study
  作者：Anna Troiani、Maurizio Speranza

  DOI：10.1021/jo971282x

  日期：1998.2.1

  The kinetics and the mechanism of the racemization and regioisomerization of O-methylated (S)-trans-4-hexen-3-ol (IS') or (R)-trans-3-hexen-2-ol (IIR') have been investigated in the gas phase at 720 Torr and in the 40-120 degrees C temperature range. The starting oxonium intermediates were generated in the gas phase by the reaction of (CH3)(2)Cl+ ions, formed by stationary gamma-radiolysis of bulk CH3Cl, on the corresponding optically active alcohols. The rate constant of the gas-phase regioisomerization of IS' ((3.4-16.0) x 10(6) s(-1)) was found to exceed that of its racemization ((1.9-9.8) x 10(6) s(-1)) over the entire temperature range. Similar differences were observed for the regioisomerization ((2.9-15.0) x 10(6) s(-1)) and the racemization of IIR' ((1.8-9.6) x 10(6) s(-1)). By analogy with previous experimental and theoretical evidence, these results are consistent with intramolecular racemization and regioisomerization processes involving the intermediacy of two distinct hydrogen-bonded complexes, wherein the CH3OH molecule is coplanarly coordinated to the in-plane hydrogens of the 1-methyl-3-ethylallyl moiety. The activation parameters for their formation from the IS' and IIR' were evaluated and compared with those concerning the racemization and regioisomerization of O-protonated (S)-trans-4-hexen-3-ol (IS), previously measured in the gas phase under similar experimental conditions. The comparison reveals that gas-phase racemization and regioisomerization of O-protonated (S)-trans-4-hexen-3-ol (1S') (AOH=H2O) involve transition structures located early along the reaction coordinate, whereas the transition structures involved in the rearrangement of O-methylated (S)-trans-4-hexen-3-ol (1S') and (R)-trans-3-hexen-2-ol (IIR') (AOH = CH3OH) are placed later along the reaction coordinate and are characterized by a strong coordination of the moving CH3OH molecule with the hydrogens of the allylic moiety.
• Chiral Ions in the Gas Phase. 1. Intramolecular Racemization and Isomerization of O-Protonated (<i>S</i>)-<i>trans</i>-4-Hexen-3-ol
  作者：Anna Troiani、Francesco Gasparrini、Felice Grandinetti、Maurizio Speranza

  DOI：10.1021/ja960212p

  日期：1997.5.1

  to the racemization and isomerization products by free 1-methyl-3-ethylallyl cations, arising from unimolecular fragmentation of excited O-protonated (S)-trans-4-hexen-3-ol (IS), was evaluated by generating them from protonation of isomeric 2,4-hexadienes and by investigating their behavior toward H218O under the same experimental conditions. The rate constant of the gas phase racemization of IS (1.4−21

  (S)-trans-4-hexen-3-ol (1S) 的酸催化外消旋和区域异构化已在气态 CH4 和 C3H8 中在 720 Torr 和 40-120 °C 温度范围内进行了研究。由激发的 O-质子化 (S)-trans-4-hexen-3-ol (IS) 的单分子断裂产生的游离 1-methyl-3-ethylallyl 阳离子对外消旋化和异构化产物的贡献通过生成它们进行评估来自异构 2,4-己二烯的质子化并通过在相同的实验条件下研究它们对 H218O 的行为。在整个温度范围内，IS 气相外消旋化的速率常数 (1.4-21.3 × 106 s-1) 超过其异构化的速率常数 (1.0-9.9 × 106 s-1)。实验结果，结合模型[C3H5+/H2O]系统的从头算理论计算，
• Palladium(II)-Catalyzed Exchange and Isomerization Reactions. 17. Exchange of Chiral Allyl Alcohols with Hydroxide, Methoxide, and Phenyl at High [Cl^-]. Stereochemistry of the Wacker Reaction
  作者：Othman Hamed、Patrick M. Henry、Charles Thompson

  DOI：10.1021/jo9906274

  日期：1999.10.1

  At high [Cl-] (> 2.0 M), PdCl42- catalyzes the exchange of chiral allylic alcohols with hydroxy, methoxy, and phenyl to give chiral allyl-substituted olefins. With unsymmetrical olefins, isomerization occurs along with exchange. The hydroxyl exchange occurs in aqueous solution while the other exchanges are carried out in methanol solution. At low [Cl-] (0.1 M) oxidation to the corresponding beta-hydroxy-, methoxy-, and phenyl-substituted carbonyl compounds occurred. The absolute configurations of the oxidation and exchange products should be the same if the same mode of addition to the Pd(II)-pi-complex is operative. The absolute configurations of the oxidation and exchange products for the phenylation reaction were the same, while for hydroxy and methoxy they were different. This result indicates methanol and water must have different stereochemistries of addition at high and low [Cl-]. Thus, previous studies showing anti hydroxypalladation at high [Cl-] are not valid indicators of the stereochemistry at low [Cl-]. If anti addition occurs at high [Cl-], the addition must be syn at low [Cl-].