1-(1,3-Dithiolane-2-ylidene)-4-phenyl-3-butene-2-one | 186707-50-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-(1,3-Dithiolane-2-ylidene)-4-phenyl-3-butene-2-one
• 英文别名: 4-phenyl-1-(1,3-dithiolane-2-ylidene)-3E-buten-2-one；(E)-1-(1,3-dithiolan-2-ylidene)-4-phenylbut-3-en-2-one
• CAS: 186707-50-6
• 化学式: C₁₃H₁₂OS₂
• 分子量: 248.37
• InChiKey: LXRJSVYYIHKOIA-VOTSOKGWSA-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：

  1-(1,3-Dithiolane-2-ylidene)-4-phenyl-3-butene-2-one 在 sodium hydroxide 、 乙二胺四乙酸 、 双氧水 、 甲基三辛基氯化铵 作用下， 以 甲苯 为溶剂， 以55%的产率得到2-[1,3]Dithiolan-2-ylidene-1-((2S,3R)-3-phenyl-oxiranyl)-ethanone
  参考文献：
  名称：

  Development of the Juliá asymmetric epoxidation reaction. Part 2. Application of the oxidation to alkyl enones, enediones and unsaturated keto esters

  摘要：

  Polyleucine-based systems have been used to catalyse the asymmetric oxidation of a variety of alkyl enones 1-4,9-14, an enynone 16 and a dienone 17 to afford the corresponding epoxides 5-8, 18-26 in good to excellent yield and optical purity. A range of enediones 30-32, 34 and one unsaturated keto ester 33 have also been epoxidised stereoselectively to afford optically active epoxides 35-39. The epoxidations were carried out with basic peroxide as the oxidant; the polyleucine catalyst was prepared from leucine N-carboxyanhydride using 1,3-diaminopropane, water (employing a humidity cabinet) or a polystyrene immobilised amine as the initiator. Preliminary mass spectral data on material derived from L-leucine and 1,3-diaminopropane (DAP-PLL) suggest that the catalyst consists of material that contains 22 +/- 10 leucine residues.

  DOI：

  10.1039/p19960002837
• 作为产物：
  描述：

  (E)-2-(1,3-dithiolan-2-ylidene)-3-oxo-5-phenylpent-4-enoic acid 在 碘 作用下， 以 二氯甲烷 为溶剂， 反应 36.0h， 以83%的产率得到1-(1,3-Dithiolane-2-ylidene)-4-phenyl-3-butene-2-one
  参考文献：
  名称：

  IODODECARBOXYLATION OF α-CARBOXYLATE, α-CINNAMOYL KETENE CYCLIC DITHIOACETALS

  摘要：

  The iododecarboxylation reaction of alpha-carboxylate, alpha-cinnamoyl ketene cyclic dithioacetals 2 was successfully performed with iodine as halogenation reagent and in water insensitive media. This reaction provides a mild and efficient method for the preparation of alpha-iodo, alpha-cinnamoyl ketene cyclic dithioacetals 3 which are important kinds of potential new intermediates to be valued.

  DOI：

  10.1081/scc-120014773

文献信息

• Synthesis of Furans and Pyrroles from 2-Alkoxy-2,3-dihydrofurans Through a Nucleophilic Substitution-Triggered Heteroaromatization
  作者：Changhui Liu、Li Zhou、Wenbo Huang、Man Wang、Yanlong Gu

  DOI：10.1002/adsc.201500993

  日期：2016.3.17

  An effective method to synthesize α‐functionalized furan and pyrrole derivatives was developed using 2‐alkoxy‐2,3‐dihydrofurans as modular precursors. This protocol featured a previously unreported tandem nucleophilic substitution/heteroaromatization reaction. Nucleophiles such as indole, α‐oxoketene dithioacetal, trimethoxybenzene, and dimethoxynaphthalene can react readily with 2‐alkoxy‐2,3‐dihydrofurans

  以2-烷氧基-2,3-二氢呋喃为模块前体，开发了一种有效的合成α-官能化呋喃和吡咯衍生物的方法。该协议的特点是以前未报道的串联亲核取代/杂芳构化反应。在酸性催化剂（例如溴化铜和铁）存在下，诸如吲哚，α-氧杂环丁烯二硫缩醛，三甲氧基苯和二甲氧基萘等亲核试剂可以轻松地与2-烷氧基-2,3-二氢呋喃反应，生成α-官能化的五元环杂环。氯化物。还讨论了该反应的机理，其中第一步是亲核取代，是触发随后的杂芳烃化的关键。该方法还可以扩展到二氢噻吩的合成。
• Copper-Catalyzed Ring-Expansion/Thiolactonization<i>via</i>Azidation of Internal Olefinic C-H Bond under Mild Conditions
  作者：Tenglong Guo、Quanbin Jiang、Zhengkun Yu

  DOI：10.1002/adsc.201600675

  日期：2016.11.3

  A copper(I)‐catalyzed, (diacetoxyiodo)benzene [PhI(OAc)2]‐mediated ring‐expansion/thiolactonization of α‐oxo ketene dithioacetals was efficiently realized via azidation of the internal olefinic C−H bond with sodium azide under mild conditions. Sequential amination, ring‐expansion rearrangement, and thiolactonization occurred to form aminated thiolactones in the presence of acetic anhydride as the additive

  通过在温和的条件下用叠氮化钠将内部C-H键与叠氮化钠叠氮化可以有效地实现铜（I）催化的（diacetoxyiodo）苯[PhI（OAc）2 ]介导的α-氧代乙烯酮二硫缩醛的扩环/硫内酯化反应条件。在使用乙酸酐作为添加剂的情况下，发生了顺序胺化，扩环重排和硫代内酯化反应，形成胺化的硫内酯，而当使用硫化铵作为还原性添加剂时，只有进行C-H胺化处理才能得到未保护的烯胺。该原位生成的乙烯基叠氮化物被证实为活性中间体，这是由苯乙炔捕获，以产生三唑。该方案为硫代内酯衍生物和未保护的烯胺提供了一条简明的途径。
• Palladium-Catalyzed Oxidative Heck-Type Allylation of β,β-Disubstituted Enones with Allyl Carbonates
  作者：Weiwei Jin、Qin Yang、Ping Wu、Jiping Chen、Zhengkun Yu

  DOI：10.1002/adsc.201400076

  日期：2014.6.16

  The palladium‐catalyzed oxidative Heck‐type allylation of β,β‐disubstituted enones, i.e., α‐oxoketene dithioacetals, was efficiently realized with allyl carbonates, providing a concise route to highly functionalized dienes. The present synthetic methodology utilizes the substrate activation strategy to activate the CH bond of β,β‐disubstituted enones by introduction of a 1,2‐dithiolane functionality

  β，β-二取代的烯酮（即α-氧杂环丁烯二硫缩醛）的钯催化氧化Heck型烯丙基化反应可通过碳酸烯丙酯有效地实现，从而为高官能化二烯的制备提供了一条简洁的途径。本合成方法利用了衬底激活策略，能活化 β的H键，β二取代烯酮通过引入的1,2-二硫戊环的功能，使烯酮基板高度极化，并由此提高其反应性，这表明对于罕见例子过渡金属催化的Heck型烯丙基化过程中的ß，ß-二取代的烯酮的烯丙基取代。
• Synthesis and Characterization of Novel Iron(0) Complexes Derived from α,β-Unsaturated-Ketone Analogues with β-Positioned Heteroatoms Containing Covalent and Coordination Bonds
  作者：Fernando Ortega-Jiménez、M. Carmen Ortega-Alfaro、José G. López-Cortés、René Gutiérrez-Pérez、Rubén A. Toscano、Luis Velasco-Ibarra、Eduardo Peña-Cabrera、Cecilio Alvarez-Toledano

  DOI：10.1021/om0004702

  日期：2000.10.1

  Synthesis of novel mono- and dinuclear complexes of Fe(0) are reported displaying both coordination and organometallic bonds. 5−11 were prepared by allowing the new ligands 1−4 to react with Fe2(CO)9. The structures of the complexes were determined by spectroscopic methods (IR, MS, HR-MS, 1H and 13C NMR) and confirmed by single-crystal X-ray analysis.

  据报道，Fe（0）的新型单核和双核配合物的合成显示出配位键和有机金属键。5 - 11分别通过允许新的配位体来制备1 - 4与铁发生反应2（CO）9。配合物的结构通过光谱法（IR，MS，HR-MS，1 H和13 C NMR）确定，并通过单晶X射线分析确认。
• DBSA-catalyzed Friedel–Crafts alkylation of cyclic ketene dithioacetals with alcohols in water
  作者：Haifeng Yu、Peiqiu Liao

  DOI：10.1016/j.tetlet.2016.05.062

  日期：2016.6

  A novel DBSA-catalyzed Friedel–Crafts alkylation of cyclic ketene dithioacetals, internal alkenes with highly nucleophilic carbon atom adjacent to the electron-withdrawing group, with alcohols in water has been developed. The reaction is efficient in the presence of catalyst loading as low as 10 mol % in water at reflux, and a wide range of alkylated ketene dithioacetals are synthesized in excellent

  已开发出一种新型的DBSA催化的环状烯酮二硫缩醛，具有高度亲核性碳原子且与吸电子基团相邻的内部烯烃与水中的醇类进行弗里德-克拉夫茨烷基化反应。在回流下在水中负载低至10 mol％的催化剂的情况下，该反应是有效的，并且以优异的产率合成了多种烷基化的烯酮二硫缩醛。