(E)-1-[1,3]Dithiolan-2-ylidene-4-phenyl-but-3-en-2-one | 116688-64-3

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: (E)-1-[1,3]Dithiolan-2-ylidene-4-phenyl-but-3-en-2-one
• 英文别名: 1-(1,3-Dithiolan-2-ylidene)-4-phenylbut-3-en-2-one；1-(1,3-dithiolan-2-ylidene)-4-phenylbut-3-en-2-one
• CAS: 116688-64-3
• 化学式: C₁₃H₁₂OS₂
• 分子量: 248.37
• InChiKey: LXRJSVYYIHKOIA-UHFFFAOYSA-N

物化性质

• 沸点：
  416.0±45.0 °C(Predicted)
• 密度：
  1.325±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  67.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  二苯甲醇 、 (E)-1-[1,3]Dithiolan-2-ylidene-4-phenyl-but-3-en-2-one 在 三氟化硼乙醚 作用下， 以 乙腈 为溶剂， 反应 0.7h， 以99%的产率得到(E)-4-(1,3-dithiolan-2-ylidene)-1,5,5-triphenylpent-1-en-3-one
  参考文献：
  名称：

  BF 3 ·Et 2 O催化α-EWG丁烯-（S，S）-缩醛和醇的直接碳-碳键形成及不对称联芳基的合成

  摘要：

  通过直接取代醇中的羟基，开发了一种高效的BF 3 ·OEt 2催化的形式脱水C-C偶联反应，该反应易于获得的α-EWG烯酮-（S，S）-乙缩醛与各种醇之间。在此C-C偶联反应的基础上，以高至优异的收率制备了一系列烷基化的α-EWG乙烯酮-（S，S）-乙缩醛和官能化的1,4-戊二烯，并以良好的收率合成了不对称联芳基通过一锅法环化芳构化过程从生成的1，4-戊二烯和硝基烷烃中提取。

  DOI：

  10.1021/jo061775e
• 作为产物：
  描述：

  1-(1,3-dithiolan-2-ylidene)propan-2-one 、 苯甲醛 在 sodium hydroxide 作用下， 以 乙醇 为溶剂， 反应 2.0h， 以95%的产率得到(E)-1-[1,3]Dithiolan-2-ylidene-4-phenyl-but-3-en-2-one
  参考文献：
  名称：

  α-Alkenoyl Ketene S,S-Acetal-Based Multicomponent Reaction: An Efficient Approach for the Selective Construction of Polyfunctionalized Cyclohexanones

  摘要：

  A versatile multicomponent reaction based on the new four-carbon synthons alpha-alkenoyl ketene S,S-acetals 1 has been developed. This three-component reaction of readily available alpha-alkenoyl ketene S,S-acetals 1 with aldehydes 2 and active methylene compounds 3 proceeds smoothly in acidic medium (glacial acetic acid in tetrahydrofuran) to give various polyfunctionalized cyclohexanones 4, 5, and 6 in a highly regio- and diastereoselective manner with good to excellent yields. The reaction can tolerate a broad range of substituents in the three components involved and is proposed to proceed via a tandem Knoevenagel-intermolecular Michael-intramolecular Michael sequence. As an extension of the synthetic application of polyfunctionalized cyclohexanones obtained, unsymmetrical biaryls 7 were synthesized in almost quantitative yields by simple transformations of the corresponding cycloadducts 6.

  DOI：

  10.1021/jo900217g

文献信息

• Ruthenium- and Rhodium-Catalyzed Chemodivergent Couplings of Ketene Dithioacetals and α-Diazo Ketones via C–H Activation/Functionalization
  作者：Manman Wang、Lingheng Kong、Qiyue Wu、Xingwei Li

  DOI：10.1021/acs.orglett.8b01890

  日期：2018.8.3

  Chemodivergent coupling of α-acylketene dithioacetals with diazo compounds has been realized under catalyst control. The Ru(II)-catalyzed C–H activation occurred at the olefinic position, and 1:2 coupling with α-diazoketoesters leads to furfurylation. In contrast, the Rh(III)-catalyzed C–H functionalization occurred at both the olefinic and the ortho C(aryl)–H positions, and [4 + 2] annulation afforded

  在催化剂控制下已经实现了α-酰基乙烯酮二硫缩醛与重氮化合物的化学发散偶联。Ru（II）催化的C–H活化发生在烯烃位置，并且与α-二重氮酮酸酯的1：2偶联导致糠醛化。相比之下，Rh（III）催化的C–H功能化同时发生在烯烃和邻位C（芳基）–H位置，[4 + 2]环烷基化提供萘酮。已经进行了合成应用以证明耦合系统的有用性。
• Palladium-Catalyzed Cross-Coupling of Internal Alkenes with Terminal Alkenes to Functionalized 1,3-Butadienes Using CH Bond Activation: Efficient Synthesis of Bicyclic Pyridones
  作者：Haifeng Yu、Weiwei Jin、Chenglin Sun、Jiping Chen、Wangmin Du、Songbo He、Zhengkun Yu

  DOI：10.1002/anie.201002737

  日期：——

  cross‐coupling of internal alkenes of α‐oxoketene dithioacetals with terminal alkenes has been successfully realized by palladium‐catalyzed CH bond activation, affording functionalized 1,3‐butadienes. Condensation of the resultant 1,3‐butadienes by diamines efficiently produced potentially bioactive bicyclic pyridone derivatives (see scheme).

  甲高度选择性直接交叉偶联与末端烯烃α-oxoketene二硫的内部烯烃的已通过钯催化的C ^成功地实现 H键活化，得到官能化的1,3-丁二烯。二胺将所得的1,3-丁二烯缩合可有效产生具有潜在生物活性的双环吡啶酮衍生物（请参见方案）。
• Palladium-catalyzed oxidative C–O cross-coupling of ketene dithioacetals and carboxylic acids
  作者：Deqiang Liang、Mang Wang、Ying Dong、Yaru Guo、Qun Liu

  DOI：10.1039/c3ra47282e

  日期：——

  Direct oxidative C–O cross-coupling reaction between active alkenes and carboxylic acids is presented. By utilizing Pd(OAc)2 as a catalyst and PhI(OAc)2 as an oxidant, ketene dithioacetals were smoothly acyloxylated in carboxylic acid–water solution, affording a variety of vinyl esters in a highly selective way with high efficiency and good functional group tolerance. A plausible mechanism is proposed that features a vinyl iodonium species as key intermediate.

  本文介绍了一种活性烯烃与羧酸之间的直接氧化 C–O 交叉偶联反应。通过使用 Pd(OAc)₂ 作为催化剂和 PhI(OAc)₂ 作为氧化剂，酮烯二硫乙酰缩醛在羧酸-水溶液中顺利地进行了酰氧基化，获得了一系列高选择性、高效率且对功能团具有良好耐受性的乙烯基酯。提出了一种合理的机制，特征是以乙烯基碘离子物种作为关键中间体。
• Formation of Benzo[<i>f</i>]-1-indanone Frameworks by Regulable Intramolecular Annulations of <i>gem</i>-Dialkylthio Trienynes
  作者：Zhongxue Fang、Ying Liu、Badru-Deen Barry、Peiqiu Liao、Xihe Bi

  DOI：10.1021/ol5034332

  日期：2015.2.20

  intramolecular annulations. The chemoselectivity of the intramolecular cyclizations can be regulated by both the base and the type of gas atmosphere used in the reaction, thus allowing the divergent synthesis of the corresponding functionalized benzo[f]-1-indanones in good to excellent yields.

  从容易获得的宝石-二烷硫基三苯炔通过分子内环化反应，已经开发出了苯并[ f ] -1-茚满酮骨架的原子经济路线。分子内环化的化学选择性可以通过反应中所用的碱和气体气氛的类型来调节，因此可以以良好至极好的收率合成相应的官能化苯并[ f ] -1-茚满酮。
• Benzyl-Type Cation Initiated Nucleophilic Substitution on Furan and Thiophene by Using α-EWG Ketene S,S-Acetals as Nucleophiles
  作者：Jun Liu、Mang Wang、Shaoguang Sun、Qun Liu

  DOI：10.1055/s-0032-1316753

  日期：2012.9

  An efficient method for introducing nucleophiles on furan and thiophene has been established via the in situ formation of benzyl-type carbocation, delocalization of the carbocation on heterocyclic ring, and nucleophilic trap of alpha-EWG ketene S,S-acetal sequence at the 5-position.