benzyl but-3-enyl sulfide | 62266-25-5

• 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: benzyl but-3-enyl sulfide
• 英文别名: 4-(benzylthio)-1-butene；Benzene, [(3-butenylthio)methyl]-；but-3-enylsulfanylmethylbenzene
• CAS: 62266-25-5
• 化学式: C₁₁H₁₄S
• 分子量: 178.298
• InChiKey: XQHOVNXSJLTKGB-UHFFFAOYSA-N

物化性质

• 沸点：
  254.2±19.0 °C(Predicted)
• 密度：
  0.985±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  12
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  25.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  benzyl but-3-enyl sulfide 在 溴 、 间氯过氧苯甲酸 作用下， 生成 3-溴四氢噻吩 1,1-二氧化物
  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：

  allyl(benzyl)sulfide 在 cesium fluoride 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 生成 benzyl but-3-enyl sulfide
  参考文献：
  名称：

  Comparison of the Reaction of Benzylammonium N-Methylides with That of Benzylsulfonium S-Methylides.

  摘要：

  通过氟离子诱导 S-苄基-S-[(三甲基硅基)甲基](烷-2-烯基)锍盐 4S 和 S-苄基-S-[(三甲基硅基)甲基](4-取代苄基)锍盐 7S 的脱硅作用，生成了烯丙基锍 S-甲基化物 8S 和二苄基锍 S-甲基化物 18S、并将异构化产物与相应的 N-甲基化物的异构化产物进行比较。S 型甲基化物 8S 选择性地向烯丙基发生重排（图 2 中的路径 a），而 N 型甲基化物 8N 则竞争性地向苄基发生重排（路径 b）。S 型甲基化物 18S 异构化为 S 型苄基化物 19S 和 20S 时，会竞争性地向苄基发生重排（图 3 中的路径 a 和 b），而 N 型甲基化物 18N 则不会发生异构化。

  DOI：

  10.1248/cpb.47.267

文献信息

• Dihydroxylation and oxidative cleavage of olefins in the presence of sulfur
  作者：Tarek Sammakia、T.Brian Hurley、Douglas M. Sammond、Randall S. Smith、Susan B. Sobolov、Thomas R. Oeschger

  DOI：10.1016/0040-4039(96)00879-9

  日期：1996.6

  The dihydroxylation of olefins using AD-mix or in the presence of sulfides has been examined as has the rate of oxidation of various classes of sulfides. The selectivity of olefin oxidation in preference to sulfur oxidation depends on the nature of the sulfur moiety, and can be problematic for certain classes of substrates.

  已经检查了使用AD-混合物或在硫化物的存在下烯烃的二羟基化，以及各种硫化物的氧化速率。烯烃氧化优先于硫氧化的选择性取决于硫部分的性质，对于某些类型的底物可能存在问题。
• Photocatalytic Activation of Elemental Sulfur Enables a Chemoselective Three-Component Thioesterification
  作者：Sho Murakami、Takeshi Nanjo、Yoshiji Takemoto

  DOI：10.1021/acs.orglett.1c02904

  日期：2021.10.1

  thioesterification using olefins, α-ketoacids, and elemental sulfur has been developed. The photocatalytic activation of elemental sulfur, a cheap and abundant sulfur source, enables the rapid installation of a sulfur atom into molecules, reactions that ordinarily would require the use of reactive and malodorous sulfur-containing compounds such as thiols and thioacids. This novel reaction is characterized

  已经开发出使用烯烃、α-酮酸和元素硫的温和且化学选择性的三组分硫酯化反应。元素硫的光催化活化是一种廉价且丰富的硫源，能够将硫原子快速安装到分子中，而这些反应通常需要使用反应性和恶臭的含硫化合物，如硫醇和硫代酸。这种新反应的特点是产量高，底物范围广，可以将硫酯部分引入复杂的分子中，包括类固醇、肽和未受保护的糖苷。机理研究表明，这种转变的成功取决于元素硫所发挥的多种作用，包括硫化剂、末端氧化剂和 HAT 介质。
• One-pot thiol-free synthetic approach to sulfides, and sulfoxides selectively
  作者：Sambasivarao Kotha、Naveen Kumar Gupta、Saima Ansari

  DOI：10.1039/d2ra04872h

  日期：——

  direct synthesis of sulfides and sulfoxides under green conditions without using any metal catalyst is reported. For this purpose, we used benzyl bromides as starting materials in the presence of potassium thioacetate (PTA) and Oxone® which are low-cost, and readily accessible chemicals. This method is highly compatible with a variety of functional groups and delivered a series of sulfides, bis-sulfides

  报道了一种简便高效的无硫醇一锅法，用于在绿色条件下不使用任何金属催化剂直接合成硫化物和亚砜。为此，我们在硫代乙酸钾 (PTA) 和 Oxone® 的存在下使用苄基溴作为起始材料，这些都是低成本且易于获得的化学品。该方法与多种官能团高度相容，并以良好的收率提供了一系列硫化物、双硫化物和亚砜。通过一种机制讨论了亚砜在砜上的选择性形成。
• Ruthenium-catalyzed intermolecular alkene–alkyne couplings in biologically relevant media
  作者：Alejandro Gutiérrez-González、Daniel Marcos-Atanes、Leonard G. Cool、Fernando López、José L. Mascareñas

  DOI：10.1039/d3sc01254a

  日期：——

  cyclopentadienyl Ru(II) catalysts can efficiently promote mild intermolecular alkyne–alkene couplings in aqueous media, even in the presence of different biomolecular components, and in complex media like DMEM. The method can also be used for the derivatization of amino acids and peptides, therefore proposing a new way to label biomolecules with external tags. This C–C bond-forming reaction, based on simple alkene

  阳离子环戊二烯基 Ru( II ) 催化剂可以有效促进水介质中温和的分子间炔烃-烯烃偶联，甚至在存在不同生物分子组分的情况下，以及在 DMEM 等复杂介质中也是如此。该方法还可用于氨基酸和肽的衍生化，从而提出了一种用外部标签标记生物分子的新方法。这种基于简单烯烃和炔烃反应物的 C-C 键形成反应现在可以添加到过渡金属催化剂促进的生物正交反应的工具箱中。
• Rh(III)-Catalyzed Diastereo- and Enantioselective Regiodivergent (Hetero)Arylamidation of (Homo)Allylic Sulfides
  作者：Xiaoyan Jia、Gui-Lin Hao、Mengxia Feng、Huanfeng Jiang、Shou-Guo Wang、Liangbin Huang

  DOI：10.1021/jacs.3c14041

  日期：2024.4.10

  rhodium-catalyzed 3-component conjunctive diastereo- and regioselective arylamidation of (homo)allylic sulfides, organon boronic acids, and dioxazolones is reported. These reactions deliver the 1,2-insertion and 2,1-insertion arylamidation products, respectively, for allylic sulfides and homoallylic sulfides. The enantioselective arylamidation of terminal and internal allylic sulfides is achieved, furnishing

  报道了（同）烯丙基硫化物、有机硼酸和二恶唑酮的铑催化三组分联合非对映和区域选择性芳基酰胺化。这些反应分别产生烯丙基硫化物和高烯丙基硫化物的 1,2-插入和 2,1-插入芳基酰胺化产物。实现了末端和内部烯丙基硫化物的对映选择性芳基酰胺化，以高产率和高非对映选择性和对映选择性提供具有一个或两个连续立构中心的各种1,3- N,S化合物。机理研究表明，由天然且易于去除的硫化物基团引起的周转限制和选择性决定步骤发生了变化。