3-(2-Ethylsulfanyl-ethyl)-4,5,6,6a-tetrahydro-1H-pentalen-2-one | 143364-17-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-(2-Ethylsulfanyl-ethyl)-4,5,6,6a-tetrahydro-1H-pentalen-2-one
• 英文别名: 3-(2-ethylsulfanylethyl)-4,5,6,6a-tetrahydro-1H-pentalen-2-one
• CAS: 143364-17-4
• 化学式: C₁₂H₁₈OS
• 分子量: 210.34
• InChiKey: FRDNKHXGGXEALH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  42.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  9-<(tert-butyl)dimethylsiloxy>-1-nonen-6-yne 在 正丁基锂 、 四丁基氟化铵 、 N-甲基吗啉氧化物 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 5.5h， 生成 3-(2-Ethylsulfanyl-ethyl)-4,5,6,6a-tetrahydro-1H-pentalen-2-one
  参考文献：
  名称：

  配位体对 Pauson-Khand 环加成的影响：中间体的捕获

  摘要：

  Pauson-Khand 钴介导的环加成反应已成为一种重要的合成反应。一些修改增加了反应的效用，包括有报道称叔胺 N-氧化物大大加快了分子内和一些分子间反应中的环加成速率。迄今为止，除了完全鉴定六羰基炔配合物之外，还没有直接证据支持热或氧化胺促进反应的机械假设。虽然氧化胺促进的反应通常比类似的热反应大大加速，但在氧化胺的存在下，1,6-烯炔的环加成速率可能会因硫、氮或氧的存在而进一步提高同炔基或双炔基位置

  DOI：

  10.1021/ja00069a017

文献信息

• Pauson–Khand reactions in water
  作者：Marie E Krafft、James A Wright、Llorente VR Boñaga

  DOI：10.1139/v05-112

  日期：2005.6.1

  We have investigated the cobalt mediated Pauson–Khand (PK) reaction in water. In the presence of detergents and surfactants, Co₂(CO)₈ and Co₄(CO)₁₂ are effective under aqueous-phase, thermal PK reactions. In a water–Triton^®X-100 medium, Co₄(CO)₁₂ is catalytically active. Further, dicobalthexacarbonyl complexes of alkynes and enynes undergo effective cyclization under thermal (70 °C) and NMO-promoted conditions. The oxidative nature of the latter conditions inhibits the reductive PK reaction. In all protocols, moderate to excellent yields of the cycloadducts are obtained. Substrates that are prone to hydrolysis, such as acetals, highly activated carboxylic acid derivatives, and those bearing propargylic heteroatom groups are tolerated under appropriate conditions. Finally, the more challenging intermolecular cycloadditions can also be easily achieved under aqueous conditions.Key words: alkyne, cycloaddition, green chemistry, Pauson–Khand reaction, water.

  我们已经在水中研究了钴介导的Pauson-Khand（PK）反应。在存在洗涤剂和表面活性剂的情况下，Co₂(CO)₈和Co₄(CO)₁₂在水相、热力PK反应中是有效的。在水-Triton® X-100介质中，Co₄(CO)₁₂具有催化活性。此外，炔烃和烯炔烃的二钴六羰基络合物在热（70°C）和NMO促进条件下进行有效的环化反应。后一条件的氧化性质抑制了还原性PK反应。在所有方案中，环加成产物的产率从中等到优良。易水解的底物，如缩醛、高度活化的羧酸衍生物以及带有丙炔基杂原子基团的底物在适当条件下是可容忍的。最后，更具挑战性的分子间环加成也可以在水相条件下轻松实现。关键词：炔烃，环加成，绿色化学，Pauson-Khand反应，水。
• Catalytic activity of dodecacarbonyltetracobalt in aqueous media: a “greening” of the Pauson–Khand reaction
  作者：Llorente V. R. Boñaga、James A. Wright、Marie E. Krafft

  DOI：10.1039/b403827d

  日期：——

  The unprecedented reactivity of Co(4)(CO)(12) with enynes under aqueous conditions, representing the development of a mild and simple aqueous-phase cobalt-catalyzed PK reaction protocol, is described herein.

  本文描述了Co（4）（CO）（12）与烯类在水相条件下的空前反应性，代表了温和简单的水相钴催化的PK反应规程的发展。
• Modification and limitations of the Livinghouse catalytic Pauson-Khand reaction
  作者：M.E. Krafft、L.V.R. Bonaga、C. Hirosawa

  DOI：10.1016/s0040-4039(99)01960-7

  日期：1999.12

  The difficult and impractical purification of Co2(CO)8 is not necessary in the catalytic thermal Pauson-Khand reaction previously described by Livinghouse.

  在Livinghouse先前描述的催化热Pauson-Khand反应中，不需要困难且不切实际地纯化Co 2（CO）8。
• Acceleration of the thermal pauson-khand reaction by coordinating ligands
  作者：Marie E. Kraff、Ian L. Scott、Romulo H. Romero

  DOI：10.1016/s0040-4039(00)74796-4

  日期：1992.6

  Coordinating ligands in the homo- and bishomopropargylic position of a 1,6-enyne have been found to enhance the rate of the thermal Pauson-Khand cycloaddition.

  已经发现在1，6-烯炔的均丙和双炔丙炔位置上的配位体可以提高热Pauson-Khand环加成的速率。
• Practical Cobalt Carbonyl Catalysis in the Thermal Pauson−Khand Reaction:  Efficiency Enhancement Using Lewis Bases
  作者：Marie E. Krafft、Llorente V. R. Boñaga、Chitaru Hirosawa

  DOI：10.1021/jo0057708

  日期：2001.5.1

  In this report we have shown that the commercially available Co-2(CO)(8) and CO4(CO)(12), and enyne-Co-2(CO)(6) complexes, are sufficiently effective in catalyzing the Pauson-Khand reaction under one atmosphere of CO pressure. It was further demonstrated that the efficiencies of these cyclization protocols could be enhanced by the presence of cyclohexylamine. These procedures have also rendered more practical and highly convenient alternatives for the catalytic Pauson-Khand reaction. Most importantly, we have dispelled the common belief that Co-4(CO)(12) is inactive in the Pauson-Khand reaction under one atmosphere of carbon monoxide. Of mechanistic importance is that these studies have also shown that the probable formation of Co-4(Co)(12) is not necessarily a dead end pathway in the Co-2(CO)(8)-catalyzed Pauson-Khand reaction. It is also of interest that substoiciometric amounts of Co-2(CO)(8), in DME and in the presence of cyclohexylamine, are sufficient for the cyclocarbonylation of enynes under a nitrogen atmosphere. Our findings have provided more practical protocols for the Pauson-Khand reaction using catalytic amounts of cobalt carbonyl complexes and a better understanding of the influence of Lewis bases on their efficiency. These reports on the activity of CO4(CO)(12) are anticipated to develop into a convenient and practical alternative for Co-2(CO)(8) catalysis.