5-(Allylthio)-1-pentyne | 166956-37-2

• 分子结构分类: 有机化合物 - 有机硫化合物 - 烯丙基硫化合物
• 英文名称: 5-(Allylthio)-1-pentyne
• 英文别名: allyl pent-4-ynyl thioether；allyl(pent-4-yn-1-yl)sulfane；5-Prop-2-enylsulfanylpent-1-yne
• CAS: 166956-37-2
• 化学式: C₈H₁₂S
• 分子量: 140.249
• InChiKey: XYFCPAOSEVEQIZ-UHFFFAOYSA-N

物化性质

• 沸点：
  194.8±23.0 °C(Predicted)
• 密度：
  0.914±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  9
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  5-(Allylthio)-1-pentyne 在 吡啶 、 ammonium molybdate 、 dichloro(pyridine-2-carboxylato)gold(III) 、 双氧水 、 氧气 、 二氯二氧化钼 、 sodium carbonate 、 copper dichloride 作用下， 以 乙醇 、 水 、 1,2-二氯乙烷 、 丙酮 、 甲苯 为溶剂， 反应 38.0h， 生成 N-[2-[tert-butyl(dimethyl)silyl]oxyethyl]-N-(4-methylphenyl)sulfonyl-1,1-dioxo-2-prop-2-enylthiolane-2-carboxamide
  参考文献：
  名称：

  金催化的酰胺类环化异构反应可得到2,2-二取代的四氢噻吩基序

  摘要：

  带有束缚的烯丙基亚砜的酰胺经过金催化的环异构化，得到四氢噻吩-2-羧酰胺及其苯并稠合的类似物。反应通过正式的7-endo-dig环化反应引发，并包含一系列不同的取代基。N-烯丙基乙酰胺的使用为新型螺环ε-内酰胺结构的开发提供了一条途径。

  DOI：

  10.1055/a-1434-4273
• 作为产物：
  描述：

  烯丙硫醇 、 5-碘-1-戊炔 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 以73%的产率得到5-(Allylthio)-1-pentyne
  参考文献：
  名称：

  A Tandem Cyclization-Onium Ylide Rearrangement-Cycloaddition Sequence for the Synthesis of Benzo-Substituted Cyclopentenones

  摘要：

  A new annulation sequence leading to benzo-substituted cyclopentenones is effected by treating o-alkynyl-substituted alpha-diazoacetophenones containing tethered heteroatoms with Rh(II) carboxylates. The reaction involves addition of the initially formed keto carbenoid onto the acetylenic pi-bond to give a rearranged vinyl carbenoid. Sulfonium ylide formation occurred both intra- and intermolecularly when the reaction was carried out in the presence of a sulfide. In the case where an ether oxygen was present on the backbone of the vinyl carbenoid, the resulting oxonium ylide underwent a [1,2]- or [2,3]-shift to give the rearranged product. These cyclic metallocarbenoids were also found to interact with a neighboring carbonyl or oximino pi-bond to produce carbonyl or azomethine ylides. The 1,3-dipoles generated in this manner were trapped with dimethyl acetylenedicarboxylate. The domino transformation was also performed intramolecularly by attaching a trapping agent directly to the carbonyl group. Incorporation of an amido carbonyl on the alkyne side chain was found to dramatically alter the course of the tandem annulation reaction. A novel rearranged cycloadduct was formed in high yield whose structure was elucidated by X-ray crystallography. The mechanism for its formation involves the opening of a transient intermediate oxabicyclo[2.2.1]heptane followed by a Wagner-Meerwein rearrangement.

  DOI：

  10.1021/jo00106a014

文献信息

• Gold- or Platinum-Catalyzed Synthesis of Sulfur Heterocycles: Access to Sulfur Ylides without Using Sacrificial Functionality
  作者：Paul W. Davies、Sébastien J.-C. Albrecht

  DOI：10.1002/anie.200904309

  日期：2009.10.19

  It′s no sacrifice: Alkynes have been used as direct precursors to sulfur ylides under gold or platinum π‐acid catalysis in an atom‐economic manner. An intramolecular redox reaction between an alkyne group with a tethered sulfoxide unit generates a sulfur ylide, which undergoes 2,3‐sigmatropic rearrangement. Acyclic substrates are cycloisomerized to afford functionalized dihydrothiophenones (see scheme)

  这不是什么牺牲：炔烃已经以原子经济的方式用作金或铂π-酸催化下硫代叶立德的直接前体。炔基与束缚的亚砜单元之间的分子内氧化还原反应产生了硫内鎓盐，其经历了2,3-σ重排。将无环底物进行环异构化以提供官能化的二氢噻吩酮（参见方案）和二氢硫吡喃酮。
• Rhodium(II)-Catalyzed Stereocontrolled Synthesis of 2-Tetrasubstituted Saturated Heterocycles from 1-Sulfonyl-1,2,3-triazoles
  作者：Alistair Boyer

  DOI：10.1021/ol5028267

  日期：2014.11.21

  Rhodium(II) acetate catalyzes the denitrogenative transformation of 4-substituted 1-sulfonyl-1,2,3-triazoles with pendent allyl and propargyl ethers and thioethers to onium ylides that undergo [2,3]-sigmatropic rearrangement to give 2-tetrasubstituted heterocycles with high yield and diastereoselectivity.
• A Tandem Cyclization-Onium Ylide Rearrangement-Cycloaddition Sequence for the Synthesis of Benzo-Substituted Cyclopentenones
  作者：Albert Padwa、Jamal M. Kassir、Mark A. Semones、M. David Weingarten

  DOI：10.1021/jo00106a014

  日期：1995.1

  A new annulation sequence leading to benzo-substituted cyclopentenones is effected by treating o-alkynyl-substituted alpha-diazoacetophenones containing tethered heteroatoms with Rh(II) carboxylates. The reaction involves addition of the initially formed keto carbenoid onto the acetylenic pi-bond to give a rearranged vinyl carbenoid. Sulfonium ylide formation occurred both intra- and intermolecularly when the reaction was carried out in the presence of a sulfide. In the case where an ether oxygen was present on the backbone of the vinyl carbenoid, the resulting oxonium ylide underwent a [1,2]- or [2,3]-shift to give the rearranged product. These cyclic metallocarbenoids were also found to interact with a neighboring carbonyl or oximino pi-bond to produce carbonyl or azomethine ylides. The 1,3-dipoles generated in this manner were trapped with dimethyl acetylenedicarboxylate. The domino transformation was also performed intramolecularly by attaching a trapping agent directly to the carbonyl group. Incorporation of an amido carbonyl on the alkyne side chain was found to dramatically alter the course of the tandem annulation reaction. A novel rearranged cycloadduct was formed in high yield whose structure was elucidated by X-ray crystallography. The mechanism for its formation involves the opening of a transient intermediate oxabicyclo[2.2.1]heptane followed by a Wagner-Meerwein rearrangement.
• Gold-Catalysed Cycloisomerisation of Ynamides To Access 2,2-Disubstituted Tetrahydrothiophene Motifs
  作者：Paul W. Davies、Parmjit Heer Kaur

  DOI：10.1055/a-1434-4273

  日期：2021.6

  Ynamides bearing a tethered allyl sulfoxide undergo a gold-catalysed cycloisomerisation to afford tetrahydrothiophene-2-carboxamides and their benzo-fused analogues. The reactions are initiated by a formal 7-endo-dig cyclisation and accommodate a range of different substituents. The use of N-allyl ynamides provided a route into novel spirocyclic ε-lactam structures.

  带有束缚的烯丙基亚砜的酰胺经过金催化的环异构化，得到四氢噻吩-2-羧酰胺及其苯并稠合的类似物。反应通过正式的7-endo-dig环化反应引发，并包含一系列不同的取代基。N-烯丙基乙酰胺的使用为新型螺环ε-内酰胺结构的开发提供了一条途径。