(S)-(-)-(Z)-3-hexen-2-ol | 148261-32-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (S)-(-)-(Z)-3-hexen-2-ol
• 英文别名: (S,Z)-hex-3-en-2-ol；(Z,2S)-hex-3-en-2-ol
• CAS: 148261-32-9
• 化学式: C₆H₁₂O
• 分子量: 100.161
• InChiKey: SMOVOSVEEFIBSP-XSIKTDMUSA-N

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：

  (S)-(-)-(Z)-3-hexen-2-ol 以 苯 为溶剂， 反应 6.5h， 生成 (Z)-(S)-[1,3-dimethyl-2-(1-methyl-pent-2-enyloxy)-2λ⁵-[1,3,2]diazaphospholidin-2-ylidene]-phosphoramidic acid diphenyl ester
  参考文献：
  名称：

  （烯丙氧基）亚氨基二氮杂磷腈的钯催化[3,3]σ重排：C-O和C-N官能团的烯丙基转座。

  摘要：

  DOI：

  10.1002/anie.200353284
• 作为产物：
  描述：

  (R)-(-)-(Z)-4-hexen-3-ol 在 lithium tetrachloropalladate 对苯醌 、 lithium chloride 作用下， 反应 0.5h， 生成 (S)-(-)-(Z)-3-hexen-2-ol
  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

文献信息

• Palladium-Catalyzed Allylic Transposition of (Allyloxy) Iminodiazaphospholidines:  A Formal [3,3]-Aza-phospha-oxa-Cope Sigmatropic Rearrangement for the Stereoselective Synthesis of Allylic Amines
  作者：Ernest E. Lee、Robert A. Batey

  DOI：10.1021/ja054161k

  日期：2005.10.1

  Pd(II)-catalyzed [3,3]-aza-phospha-oxa-Cope rearrangement then gives a phosphoramide, which is readily hydrolyzed under acidic conditions to yield allylic amine derivatives. Pd(II) catalysis is believed to occur in a fashion analogous to that of the rearrangement of allylic imidates. The scope of racemic, diastereoselective, and enantioselective variants of this rearrangement is described. The use of chiral diamine

  N-保护的烯丙胺的合成是利用钯 (II) 催化的（烯丙氧基）亚氨基二氮杂膦的 [3,3]-重排实现的。这种 [3,3]-氮杂-磷杂-氧杂-Cope sigmatropic 重排反应在热力学上由 P=N 到 P=O 的互变驱动，是 Overman 重排的替代方法。整个过程包括将烯丙醇亲核置换到 P(III) 前体上，然后进行施陶丁格反应以生成（烯丙氧基）亚氨基二氮杂磷脂前体。Pd(II)-催化的[3,3]-氮杂-磷-氧杂-Cope重排然后产生磷酰胺，其在酸性条件下容易水解以产生烯丙胺衍生物。据信，Pd(II) 催化以类似于烯丙基亚氨酸酯重排的方式发生。外消旋的范围，描述了这种重排的非对映选择性和对映选择性变体。报道了手性二胺助剂在非对映选择性重排中的使用。手性 N,N'-二甲基环己二胺衍生的二氮杂磷脂的重排产生具有中等非对映选择性（高达 3.5:1 dr）的磷酰胺。无论起始烯丙醇几何结构如何
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