(E)-3-(p-toluenesulfonyl)-2-propene-1-ol | 95314-83-3

• 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: (E)-3-(p-toluenesulfonyl)-2-propene-1-ol
• 英文别名: (E)-1-(p-Tolylsulfonyl)-1-propen-3-ol；(E)-3-(4-methylphenyl)sulfonylprop-2-en-1-ol
• CAS: 95314-83-3
• 化学式: C₁₀H₁₂O₃S
• 分子量: 212.269
• InChiKey: AYZRKHJQRPFEKB-KRXBUXKQSA-N

物化性质

• 熔点：
  120-121 °C
• 沸点：
  427.3±45.0 °C(Predicted)
• 密度：
  1.236±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  62.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-3-(p-toluenesulfonyl)-2-propene-1-ol 在 吡啶 、 三溴化磷 作用下， 以 二氯甲烷 为溶剂， 以54%的产率得到E-3-溴-1-(对甲苯磺酰基)丙烯
  参考文献：
  名称：

  “Syn-Effect” in the Conversion of (E)-Vinylic Sulfones to the Corresponding Allylic Sulfones

  摘要：

  研究发现，在温和条件下通过碱性处理，(E)-乙烯基砜类化合物倾向于优先形成动力学控制的(Z)-烯丙基砜类产物，而(Z)-乙烯基砜则生成(E)-烯丙基砜。这种立体化学关系可通过“邻位效应”来解释，并且通过观察相应的γ-单取代或γ,γ-双取代乙烯基砜所生成的烯丙基砜的E/Z比率，确定了不同取代基的相对程度如下：RO–（R=CH3, C2H5）＞ ArO–（Ar=p-CH3OC6H4, p-CH3C6H4, C6H5, p-NO2C6H4）≥ AcO–＞ Cl– ≥ Br–＞ CH3–＞ CH3S– ≥ –CH2–（环状和非环状）＞(CH3)2CH–>＞(CH3)3C–, C6H5–。对一些乙烯基砜进行了X射线晶体学分析，以揭示“邻位效应”的起源。

  DOI：

  10.1246/bcsj.65.75
• 作为产物：
  描述：

  acetoxy-1 p-toluenesulfonyl-3 propene-2 在 盐酸 作用下， 以 甲醇 为溶剂， 反应 48.0h， 以92%的产率得到(E)-3-(p-toluenesulfonyl)-2-propene-1-ol
  参考文献：
  名称：

  钯 (II) 催化的 2-烯基对甲苯基砜的乙酰氧基化和氯化

  摘要：

  2-烯基对甲苯基砜通过 π-烯丙基钯配合物转化为相应的 3-乙酰氧基（或氯）-1-烯基对甲苯基砜，该配合物在 Cu 存在下与乙酸根阴离子或氯阴离子等亲核试剂发生区域特异性反应（二）。

  DOI：

  10.1246/bcsj.57.1092

文献信息

• A Facile Regio- and Stereocontrolled Synthesis of (E)-Disubstituted Vinyl Sulfones <i>via</i> Transformation of Alkenylzirconocenes with Sulfonyl Chlorides
  作者：De-Hui Duan、Xian Huang

  DOI：10.1055/s-1999-2616

  日期：1999.3

  Alkenylzirconium reagents, readily obtained by hydrozirconation of terminal alkynes, can smoothly react with sulfonyl chlorides to afford (E)-disubstituted vinyl sulfones in moderate to good yields. Some γ-functionalized vinyl sulfones can be also conveniently synthesized.

  烯基锆试剂通过终端炔烃的氢锆化很容易获得，可以与磺酰氯顺利反应，生成中等到良好产率的（E）-二取代乙烯磺酮。此外，一些γ-功能化乙烯磺酮也可以方便地合成。
• Polyethylene glycol (PEG) 4000 catalysed regioselective nucleophilic ring opening of oxiranes - A new and convenient synthesis of β-hydroxy sulfone and β-hydroxy sulfide
  作者：A.K. Maiti、P. Bhattacharyya

  DOI：10.1016/s0040-4020(01)89588-0

  日期：1994.1

  Oxiranes and sodium p-toluene sulfinate salt react smoothly in a regioselective manner in the presence of PEG4000 to furnish β-hydroxy sulfone and β-hydroxysuifide. The reaction was extended for the preparation of alkylsulfones and β-oxosulfones from alkylhalide and β-oxohalide respectively.

  环氧乙烷酮和对甲苯亚磺酸钠在PEG4000存在下以区域选择性的方式平稳反应，从而提供β-羟基砜和β-羟基亚砜。扩展反应以分别由烷基卤和β-氧代卤化物制备烷基砜和β-氧代砜。
• Palladium-catalyzed allylic oxidation of 1-(p-toluenesulfonyl)-2-propene and 1-(trimethylsilyl)-1-(p-toluenesulfonyl)-2-propene
  作者：Jacques Muzart、Jean-Pierre Pete、Abdelkhalek Riahi

  DOI：10.1016/s0022-328x(00)98919-8

  日期：1987.9

  The course of palladium-catalyzed oxidation of a terminal alkene by t-BuOOH or by O2/H2O is greatly modified when the allylic carbon bears a p-toluenesulfonyl substituent, and allylic oxidation results. Mechanistic explanations of this observation are proposed.

  当烯丙基碳带有对甲苯磺酰基取代基时，t-BuOOH或O 2 / H 2 O对钯催化的末端烯烃的氧化过程大大地改变了，并导致了烯丙基氧化。建议对此现象进行机械解释。
• Stereoselective formation of α-fluoro-α-trifluoromethyl-γ-lactones starting from γ-hydroxy-α,β-unsaturated sulfones and a hexafluoropropene-diethylamine adduct (PPDA)
  作者：Katsuyuki Ogura、Ken-ichi Ogu、Takashi Ayabe、Jun-ichi Sonehara、Motohiro Akazome

  DOI：10.1016/s0040-4039(97)01120-9

  日期：1997.7

  (E)-3-Hydroxy-1-alkenyl p-tolyl sulfones (1) reacted with a hexafluoropropen-diethylamine adduct (PPDA) to afford alpha-fluoro-alpha-(trifluoromethyl)-beta-[(p-tolylsulfonyl)methyl]-gamma-lactones (2). This reaction is so stereoselective that only one diastereomer of 2 is detected in the reaction mixture. A plausible mechanism for this intriguing reaction is discussed. (C) 1997 Elsevier Science Ltd.

  (E)-3-羟基-1-烯丙基二甲苯 sulfonyl 化物 (1) 与六氟丙二胺加成物 (PPDA) 反应，生成 alpha-氟基-α-( trifluoromethyl ) -beta-[(p-甲基苯 sulfonyl )甲基]-gamma-环状物 (2)。本反应如此立体选择性，反应体系中只能检测到产物 2 的一种对映异构。对于这一引人注目的反应，提出了一个合理的机制。 (C) 1997 Elsevier Science Ltd.
• One-Step Palladium-Catalyzed Synthesis of Substituted Dihydrofurans from the Carbonate Derivatives of γ-Hydroxy-α,β-unsaturated Sulfones
  作者：José L. Garrido、Inés Alonso、Juan C. Carretero

  DOI：10.1021/jo981391r

  日期：1998.12.1

  The palladium-catalyzed nucleophilic allylic substitution of the carbonate derivatives of gamma-hydroxy-alpha,beta-unsaturated sulfones (2) with soft carbon nucleophiles such as malonates, beta-keto esters, 1,3-diketones, and alpha-sulfonyl ketones took place cleanly and with full regiocontrol (gamma-substitution). Typical optimized conditions are Pd-2(dba)(3) (5 mol %), dppe (20 mol %), molecular sieves, in toluene-THF at 100 degrees C. Unexpectedly, when beta-keto esters, 1,3-diketones, and alpha-sulfonyl ketones were used as nucleophiles a cascade process occurred, via initial gamma-regioselective allylic substitution and further intramolecular conjugate addition of the enol moiety to the alpha,beta-unsaturated sulfone, to give 2,3,4,5-tetrasubstituted dihydrofurans (13-25) in moderate to good yields. Moreover, the cyclization step is highly stereoselective giving predominantly or exclusively the 4,5-dihydrofuran of trans configuration. From readily available enantiopure (S)-2, this one-step procedure of synthesis of substituted dihydrofurans has been applied to the synthesis of enantiomerically pure tetrasubstituted tetrahydrofurans.