(2S)-hex-3-en-2-ol | 148261-31-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2S)-hex-3-en-2-ol
• 英文别名: (E,2S)-hex-3-en-2-ol
• CAS: 148261-31-8
• 化学式: C₆H₁₂O
• 分子量: 100.161
• InChiKey: SMOVOSVEEFIBSP-OVCGOVNKSA-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：

  (2S)-hex-3-en-2-ol 在 盐酸 、 双(乙腈)氯化钯(II) 作用下， 以 四氢呋喃 、 二氯甲烷 、 苯 为溶剂， 反应 22.25h， 生成 (E)-(S)-N-(1-ethyl-but-2-enyl)-4-methyl-benzenesulfonamide
  参考文献：
  名称：

  钯催化的（烯丙氧基）亚氨基二氮杂膦的烯丙基转座：用于立体选择性合成烯丙胺的正式 [3,3]-Aza-phospha-oxa-Cope Sigmatropic 重排

  摘要：

  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

  DOI：

  10.1021/ja054161k
• 作为产物：
  描述：

  (S,R)-反式-3-己烯-2-醇 生成 (2S)-hex-3-en-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

• Palladium-Catalyzed[3,3] Sigmatropic Rearrangement of (Allyloxy)iminodiazaphospholidines: Allylic Transposition of CO and CN Functionality
  作者：Ernest E. Lee、Robert A. Batey

  DOI：10.1002/anie.200353284

  日期：2004.3.26
• Iterative enolate Claisen rearrangements: versatile route to optically pure 2,7-nonadiene-5-carboxylic acids
  作者：John C. McKew、Mark J. Kurth

  DOI：10.1021/jo00069a019

  日期：1993.8

  A short, versatile, and diastereoselective method of preparing 2,7-nonadiene-5-carboxylic acids by an iterative enolate Claisen rearrangement procedure has been developed. Homochiral (E)- and (Z) secondary allylic alcohols 1-4, prepared from (S)-(-)-ethyl lactate, were esterified with acetic acid and enolized, and the resulting silyl ketene acetals were warmed to room temperature to effect [3,3]-sigmatropic rearrangement to 4-hexenoic acids 5-8. Esterification of these acids with alcohols 1-4 followed by a second enolate Claisen rearrangement delivered the targeted 2,7-nonadiene-5-carboxylic acids with high diastereoselectivity. This second [3,3]-sigmatropic rearrangement provides well-placed and potentially synthetically useful functionality and stereochemistry.
• Regio- and Stereochemistry of Gas-Phase Acid-Induced Nucleophilic Substitutions on Chiral Allylic Alcohols¹
  作者：Maurizio Speranza、Anna Troiani

  DOI：10.1021/jo971283p

  日期：1998.2.1

  The regio- and stereochemistry of the nucleophilic attack of (S)-trans-3-hexen-2-ol (M-s) and (S)-trans-4-hexen-3-ol (E-s) on the corresponding O-protonated (L = H) and -methylated (L = CH3) derivatives (MsL+ and EsL+) are investigated in the gas phase at 40 degrees C (720 Torr). The MsL+ and EsL+ intermediates are produced in the gas phase by the attack of the ionic Bronsted and Lewis acids, formed by stationary gamma-radiolysis of bulk CH3Cl, on the corresponding chiral alcohols, i.e., M-s and E-s. In these systems, firm evidence in favor of the concerted S(N)2' pathway, accompanying the classical S(N)2 one, is obtained by excluding the following: (i) the isomerization of MsL+ (or EsL+) before the attack by the nucleophile NuH = M-s (or E-s); (ii) the isomerization of the (C6H11)(2)OH+ substitution intermediates before neutralization; (iii) the intermediacy of allylic cations. The regioselectivity factors (S(N)2'/S(N)2 = 1.4 (M-s), 1.1(E-s)) confirm previous experimental and theoretical evidence about the prevalence in the gas phase of the S(N)2' pathway, over the competing S(N)2 one. Orientation of NuH by MsL+ (or EsL+) determines the regiochemistry of the allylic substitution, When NuH approaches the oxonium intermediate from the direction syn to the leaving moiety LOH, a frontside S(N)2 displacement takes places favored by preliminary proton bonding between LOH and NuH. The S(N)2' reaction instead follows attack on the pi-LUMO of the oxonium ion by the NuH juxtaposed anti to the leaving LOH group. Observation of a predominant anti-S(N)2' orientation provides the first experimental basis of modern concepts pointing to Coulombic interactions as the main intrinsic factors governing the S(N)2' stereochemistry and to solvation and ion pairing as the factors determining the low efficiency of S(N)2' reactions and their preferred syn stereochemistry in solution.