3-(2,2,2-trifluoroethylidene)-2,4-dithiapentane 2-oxide | 1225456-74-5

• 分子结构分类: 有机化合物 - 有机硫化合物 - 亚砜
• 英文名称: 3-(2,2,2-trifluoroethylidene)-2,4-dithiapentane 2-oxide
• 英文别名: 2-trifluoromethyl-1-methylsulfanyl-1-methylsulfinylethene；3,3,3-Trifluoro-1-methylsulfanyl-1-methylsulfinylprop-1-ene
• CAS: 1225456-74-5
• 化学式: C₅H₇F₃OS₂
• 分子量: 204.237
• InChiKey: CGAKAEHELLUFCH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  61.6
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3-叔丁基苯酚 、 3-(2,2,2-trifluoroethylidene)-2,4-dithiapentane 2-oxide 在 三氟甲磺酸酐 作用下， 以 二氯甲烷 为溶剂， 以76%的产率得到6-tert-butyl-2-methylthio-3-trifluoromethylbenzo[b]furan
  参考文献：
  名称：

  由酚类通过直接正位官能化反应合成 3-三氟甲基苯并[b]呋喃

  摘要：

  已经设计了一种简洁且面向多样性的三氟甲基苯并 [b] 呋喃路线。通过新的三氟甲磺酸酐介导的延长 Pummerer 环化反应与三氟甲基乙烯酮二硫代乙缩醛一氧化物，多种酚类直接转化为相应的 2-甲硫基-3-三氟甲基苯并 [b] 呋喃。产物的甲硫基经过进一步的转变，增加了可用三氟甲基苯并[b]呋喃的多样性。

  DOI：

  10.1021/ja1030134

文献信息

• Facile Synthesis of Multisubstituted Benzo[<i>b</i>]furans via 2,3-Disubstituted 6,7-Furanobenzynes Generated from <i>ortho</i>-Iodoaryl Triflate-type Precursors
  作者：Takamoto Morita、Yoshitake Nishiyama、Suguru Yoshida、Takamitsu Hosoya

  DOI：10.1246/cl.160951

  日期：2017.1.5

  a highly regioselective manner. Since a variety of precursors were easily synthesizable from readily available 2,3-disubstituted 6-hydroxybenzofurans, this method enabled facile synthesis of a wide range of multisubstituted benzofurans, including π-extended molecules.

  使用甲硅烷基甲基格氏试剂作为活化剂，从邻碘芳基三氟甲磺酸酯型前体有效生成 2,3-二取代的 6,7-呋喃苯乙炔。6,7-呋喃苯乙炔和不对称亲芳体之间的反应以高度区域选择性的方式进行。由于各种前体很容易从容易获得的 2,3-二取代 6-羟基苯并呋喃合成，该方法能够轻松合成多种多取代苯并呋喃，包括 π 扩展分子。
• Reaction of 2-(2,2,2-Trifluoroethylidene)-1,3-dithiane 1-Oxide with Ketones under Pummerer Conditions and Its Application to the Synthesis of 3-Trifluoromethyl-Substituted Five-Membered Heteroarenes
  作者：Takayuki Kobatake、Suguru Yoshida、Hideki Yorimitsu、Koichiro Oshima

  DOI：10.1002/anie.200906774

  日期：2010.3.22

  Easy as pie: With the aid of triflic anhydride, the title reaction resulted in nucleophilic attack of the carbonyl oxygen atom onto the activated cationic sulfur center and subsequent [3,3]‐sigmatropic rearrangement (see scheme). The products are precursors of the difficult‐to‐synthesize five‐membered 3‐trifluoromethyl heteroarene compounds.

  简单易用：借助三氟甲磺酸酐，标题反应导致羰基氧原子亲核攻击活化的阳离子硫中心，并随后发生[3,3]-σ重排（请参见方案）。该产品是难于合成的五元3-三氟甲基杂芳烃化合物的前体。
• Two-Step, Practical, and Diversity-Oriented Synthesis of Multisubstituted Benzofurans from Phenols through Pummerer Annulation Followed by Cross-coupling
  作者：Kei Murakami、Hideki Yorimitsu、Atsuhiro Osuka

  DOI：10.1246/bcsj.20140241

  日期：2014.12.15

  Practical and diversity-oriented synthesis of multisubstituted benzofurans has been accomplished from simple phenols through a Pummerer annulation/cross-coupling sequence. Operationally simple and rapid reactions of phenols with ketene dithioacetal monoxides (KDMs) with the aid of trifluoroacetic anhydride provide the corresponding 2-methylsulfanylbenzo[b]furans. The scope of the reaction encompasses phenols and KDMs having a broad range of substituents. The remaining methylsulfanyl group in the annulation products is converted to various aryl groups through cross-coupling reactions that we improved specially to this end. This two-step approach to multisubstituted benzofurans is powerful enough to synthesize highly fluorescent benzofuran derivatives as well as the naturally occurring Eupomatenoid family.

  已成功实现从简单酚类化合物合成多取代苯并呋喃的实用且多样化的合成方法，采用了Pummerer环化/交叉偶联序列。酚类与酮硫酰单氧化物（KDMs）在三氟乙酸酐的帮助下发生操作简便、迅速的反应，生成相应的2-甲基硫苯并[b]呋喃。该反应的适用范围涵盖了具有广泛取代基的酚类和KDMs。环化产物中的剩余甲基硫基团通过我们特别改进的交叉偶联反应转化为各种芳基。此两步法合成多取代苯并呋喃的能力足以合成高度荧光的苯并呋喃衍生物，以及天然存在的Eupomatenoid家族。
• Practical, Modular, and General Synthesis of Benzofurans through Extended Pummerer Annulation/Cross-Coupling Strategy
  作者：Kei Murakami、Hideki Yorimitsu、Atsuhiro Osuka

  DOI：10.1002/anie.201403288

  日期：2014.7.14

  Operationally simple, efficient, and widely applicable Pummerer annulations of simple phenols with ketene dithioacetal monoxides, with the aid of trifluoroacetic anhydride, have been shown to provide a variety of benzofurans having a methylthio group at the 2‐position. Subsequent and newly developed nickel‐catalyzed arylation at the methylthio group culminates in diversity‐oriented synthesis of multisubstituted

  已证明在三氟乙酸酐的帮助下，简单酚的操作简单，有效且广泛适用的Pummerer环化与乙烯酮二硫缩醛一氧化碳可提供多种在2位具有甲硫基的苯并呋喃。随后和新开发的甲硫基镍催化的芳基化反应最终导致了多取代苯并呋喃的多样性导向合成。我们扩展的Pummerer环空/交叉耦合序列功能强大，足以合成具有生物活性的天然产物以及高荧光性的苯并呋喃衍生物。
• Synthesis of a Library of Fluorescent 2-Aryl-3-trifluoromethylnaphthofurans from Naphthols by Using a Sequential Pummerer-Annulation/Cross-Coupling Strategy and their Photophysical Properties
  作者：Yuuya Ookubo、Atsushi Wakamiya、Hideki Yorimitsu、Atsuhiro Osuka

  DOI：10.1002/chem.201201261

  日期：2012.10.1

  was the most efficient catalyst for the arylation step, which represents the first cross‐coupling of aryl sulfides by using an N‐heterocyclic‐carbene‐ligated palladium complex. This library consists of new π‐expanded molecules, all of which are fluorescent in the solid state as well as in solution. Their photophysical properties, such as absorption and emission, fluorescence quantum yields, and fluorescence

  从简单的萘酚中高效合成了2-芳基-3-三氟甲基萘呋喃文库。在该合成中，萘酚与3-（2,2,2-三氟亚乙基）-2-，4-二硫杂戊烷2-氧化物的Pummerer型环化后，将所得的2-甲硫基-3-三氟甲基萘呋喃与各种芳基锌试剂。钯配合物Pd-PEPPSI-IPr是芳基化步骤中最有效的催化剂，代表了使用N-杂环-卡宾连接的钯配合物实现的芳基硫醚的首次交叉偶联。该文库由新的π扩展分子组成，所有这些分子在固态和溶液中均发出荧光。对其吸收和发射，荧光量子产率和荧光寿命等光物理性质进行了彻底的研究。