(E)-1-[1,3]Dithiolan-2-ylidene-4-p-tolyl-but-3-en-2-one | 238434-86-1

• 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-p-tolyl-but-3-en-2-one
• 英文别名: 1-(1,3-Dithiolan-2-ylidene)-4-(4-methylphenyl)but-3-en-2-one；1-(1,3-dithiolan-2-ylidene)-4-(4-methylphenyl)but-3-en-2-one
• CAS: 238434-86-1
• 化学式: C₁₄H₁₄OS₂
• 分子量: 262.397
• InChiKey: MMTDHRRRYCKXSK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.21
• 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：

  (E)-1-[1,3]Dithiolan-2-ylidene-4-p-tolyl-but-3-en-2-one 、 二苯甲醇 在 三氟化硼乙醚 作用下， 以 乙腈 为溶剂， 反应 0.5h， 以99%的产率得到(E)-4-(1,3-dithiolan-2-ylidene)-5,5-diphenyl-1-(p-tolyl)pent-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 、 对甲基苯甲醛 在 sodium hydroxide 作用下， 以 乙醇 为溶剂， 反应 2.0h， 以93%的产率得到(E)-1-[1,3]Dithiolan-2-ylidene-4-p-tolyl-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

• Unmasking Dipole Character of Acyl Ketene Dithioacetals via a Cascade Reaction with Arynes: Synthesis of Benzo[<i>b</i>]thiophenes
  作者：Parul Garg、Anand Singh

  DOI：10.1021/acs.orglett.8b00053

  日期：2018.3.2

  An unusual strategy toward novel substituted benzo[b]thiophenes has been developed. The generation of arynes in the presence of acyl ketene dithioacetals resulted in a cascade reaction involving [3 + 2] cycloaddition, and a dealkylative arylation of a thioether moiety to afford 2,3-disubstuted benzo[b]thiophenes. This route represents an expeditious approach to benzothiophenes that employs acyl ketene

  已经开发出一种针对新型取代的苯并[ b ]噻吩的不寻常策略。在酰基乙烯酮二硫缩醛的存在下生成芳烃导致级联反应，涉及[3 + 2]环加成反应，以及硫醚部分的脱烷基芳基化反应，得到2,3-二取代的苯并[ b ]噻吩。该途径代表了采用酰基乙烯酮二硫缩醛作为偶极子的苯并噻吩的一种快速方法。
• 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。
• BF₃·Et₂O-Catalyzed Direct Carbon−Carbon Bond Formation of α-EWG Ketene-(<i>S</i>,<i>S</i>)-Acetals and Alcohols and Synthesis of Unsymmetrical Biaryls
  作者：Qian Zhang、Shaoguang Sun、Jianglei Hu、Qun Liu、Jing Tan

  DOI：10.1021/jo061775e

  日期：2007.1.1

  efficient BF3·OEt2-catalyzed formal dehydration C−C coupling reaction between readily available α-EWG ketene-(S,S)-acetals and various alcohols via direct substitution of the hydroxy group in alcohols has been developed. On the basis of this C−C coupling reaction, a series of alkylated α-EWG ketene-(S,S)-acetals and functionalized 1,4-pentanedienes were prepared in high to excellent yields and the unsymmetrical

  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。
• α-Alkenoyl Ketene <i>S</i>,<i>S</i>-Acetal-Based Multicomponent Reaction: An Efficient Approach for the Selective Construction of Polyfunctionalized Cyclohexanones
  作者：Yuhui Ma、Mang Wang、Dan Li、Bahargul Bekturhun、Jun Liu、Qun Liu

  DOI：10.1021/jo900217g

  日期：2009.4.17

  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.