(E)-5-phenylpent-4-en-1-yl 4-methylbenzenesulfonate | 13159-18-7

• 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)-5-phenylpent-4-en-1-yl 4-methylbenzenesulfonate
• 英文别名: (E)-5-phenylpent-4-enyl 4-methylbenzenesulfonate；(E)-1-phenyl-5-(p-toluenesulfonyloxy)-1-pentene；Toluol-4-sulfonsaeure-<5t-phenyl-pent-4-enylester>；Toluol-4-sulfonsaeure-(5t-phenyl-pent-4-enylester)；4-Penten-1-ol, 5-phenyl-, 1-(4-methylbenzenesulfonate), (4E)-；[(E)-5-phenylpent-4-enyl] 4-methylbenzenesulfonate
• CAS: 13159-18-7
• 化学式: C₁₈H₂₀O₃S
• 分子量: 316.421
• InChiKey: BDNGTCGXMAKOHF-UXBLZVDNSA-N

物化性质

• 沸点：
  484.4±34.0 °C(Predicted)
• 密度：
  1.162±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  22
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  51.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-5-phenylpent-4-en-1-yl 4-methylbenzenesulfonate 在 sodium hydroxide 、 sodium iodide 作用下， 以 甲醇 、 丙酮 为溶剂， 反应 24.0h， 生成 (E)-5-(benzylthio)-1-phenyl-1-pentene
  参考文献：
  名称：

  Regiochemical and stereochemical studies on halocyclization reactions of unsaturated sulfides

  摘要：

  The regiochemistry and stereochemistry for the halocyclization reactions of unsaturated benzyl sulfides have been examined as a function of tether length, type of unsaturation (carbon-carbon double bond versus carbon-carbon triple bond), substituents, and halogenating agent. Alkenyl sulfides were found to react with iodine or bromine at room temperature to give five-membered ring cycloadducts exclusively over those having four-membered rings, while for larger systems, six-membered ring products are formed preferentially over their five-membered ring isomers and exclusively over the seven-membered ring adducts. The endo- versus exo-regioselectivity of these alkenyl sulfide ring closures most likely reflects the difference in thermodynamic stabilities of the beta-halo sulfide cycloadducts, which are able to equilibrate via a common episulfonium intermediate. The efficiency of the cyclization process markedly drops off for these alkenyl sulfides as the tether length increases beyond four intervening carbon centers. Thus, while the halogenations of 3-butenyl sulfides and 4-pentenyl sulfides give high yields of cycloadducts, those of 5-hexenyl sulfides afford only small amounts of cyclized products and large quantities of acyclic dibromides. Conversely the reactions of acetylenic sulfides with iodine give uniformly high yields and regiochemical control regardless of the tether length. Thus, 3-butynyl and 4-pentynyl sulfides cyclize cleanly to the five-membered ring while 5-hexynyl sulfides give exclusively the six-membered ring, The products arising from these alkynyl sulfide ring closures are believed to be formed under kinetic control. The methodology has been applied to the synthesis of unusual bicyclic beta-lactams related to the penicillin family of antibiotics.

  DOI：

  10.1021/jo00125a038
• 作为产物：
  描述：

  5-苯基-4-戊烯酸 在 吡啶 、 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 生成 (E)-5-phenylpent-4-en-1-yl 4-methylbenzenesulfonate
  参考文献：
  名称：

  Basselier,J.-J. et al., Bulletin de la Societe Chimique de France, 1965, p. 2988 - 2994

  摘要：

  DOI：

文献信息

• Palladium-Catalyzed Allylic Cross-Coupling Reactions of Primary and Secondary Homoallylic Electrophiles
  作者：Benjamin J. Stokes、Susanne M. Opra、Matthew S. Sigman

  DOI：10.1021/ja305403s

  日期：2012.7.18

  cross-coupling of homoallylic tosylate substrates using boronic acids and pinacol esters is reported. The reaction uses 2-(4,5-dihydro-2-oxazolyl)quinoline (quinox) as a ligand and is performed at ambient temperature. The scope of the reaction is broad in terms of both the boronate transmetalating reagent and the substrate and includes secondary tosylates. Mechanistic studies support an alkene-mediated

  报道了使用硼酸和频哪醇酯的 Pd(0) 催化的高烯丙基甲苯磺酸酯底物的烯丙基交叉偶联。该反应使用 2-(4,5-二氢-2-恶唑基) 喹啉 (quinox) 作为配体并在环境温度下进行。就硼酸盐金属转移试剂和底物而言，反应范围很广，包括甲苯磺酸仲酯。机理研究支持未活化的初级和次级烷基甲苯磺酸盐的烯烃介导的 S(N)2 型立体转化氧化加成。
• Pd(quinox)-catalyzed allylic relay Suzuki reactions of secondary homostyrenyl tosylates via alkene-assisted oxidative addition
  作者：Benjamin J. Stokes、Amanda J. Bischoff、Matthew S. Sigman

  DOI：10.1039/c4sc00602j

  日期：——

  relay Suzuki cross-coupling reactions of secondary alkyl tosylates, featuring a sterically-hindered oxidative addition and precise control of β-hydride elimination, are reported. The identification of a linear free energy relationship between the relative rates of substrate consumption and the electronic nature of the substrate alkene suggests that the oxidative addition requires direct alkene involvement

  据报道，Pd 催化的甲苯磺酸仲烷基酯的烯丙基继电器 Suzuki 交叉偶联反应具有空间位阻氧化加成和β-氢化物消除的精确控制。底物消耗的相对速率与底物烯烃的电子性质之间线性自由能关系的确定表明氧化加成需要烯烃的直接参与。烷基链长度对反应结果影响的研究支持螯合控制的氧化加成。
• New method for the synthesis of α-substituted tetrahydrofuran-2-methanols through diastereoselective addition of THF to aldehydes mediated by Et3B in the presence of air
  作者：Takehiko Yoshimitsu、Maki Tsunoda、Hiroto Nagaoka

  DOI：10.1039/a904745j

  日期：——

  The tetrahydrofuranyl radical, generated from THF with Et3B in the presence of air, was found to react with aldehydes threo-selectively to afford α-substituted tetrahydrofuran-2-methanols, the common structural motifs of biologically active acetogenin polyketides, in moderate yields.

  研究发现，在空气存在下，四氢呋喃自由基与 Et3B 从 THF 中生成的四氢呋喃自由基可与醛发生三选择性反应，以中等产量生成δ-取代的四氢呋喃-2-甲醇，这是具有生物活性的乙酰苷元多酮类化合物的常见结构基团。
• Ligand‐Dictated Regiodivergent Allylic Functionalizations via Palladium‐Catalyzed Remote Substitution
  作者：Xin Wang、Han-Zhe Miao、Guo-Qiang Lin、Zhi-Tao He

  DOI：10.1002/anie.202301556

  日期：——

  Palladium-catalyzed regiodivergent allylic C−H functionalizations were established via remote substitution, which provides a novel model for the seldomly studied migratory Tsuji–Trost reaction. 1,4-Hydrofunctionalization of a conjugated diene intermediate was demonstrated to be feasible via a newly synthesized bisphosphine ligand.

  通过远程取代建立了钯催化的区域分散烯丙基 C−H 官能化，这为很少研究的迁移 Tsuji-Trost 反应提供了一个新模型。通过新合成的双膦配体，共轭二烯中间体的 1,4-氢官能化被证明是可行的。
• Riobe,O., Comptes Rendus des Seances de l'Academie des Sciences, Serie C: Sciences Chimiques, 1967, vol. 264, p. 109 - 111
  作者：Riobe,O.

  DOI：——

  日期：——