2-(phenylsulfinyl)cyclopenten-2-one | 84978-79-0

• 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: 2-(phenylsulfinyl)cyclopenten-2-one
• 英文别名: 2-(phenylsulfinyl)cyclopent-2-enone；2-(phenylsulfinyl)cyclopent-2-en-1-one；2-(Benzenesulfinyl)cyclopent-2-en-1-one
• CAS: 84978-79-0
• 化学式: C₁₁H₁₀O₂S
• 分子量: 206.265
• InChiKey: ZFDJQSZRPUWZRO-UHFFFAOYSA-N

物化性质

• 沸点：
  461.4±44.0 °C(Predicted)
• 密度：
  1.33±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  53.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(phenylsulfinyl)cyclopenten-2-one 以 四氢呋喃 为溶剂， 生成 3-甲基-2-环戊烯-1-酮
  参考文献：
  名称：

  The sila-Pummerer reaction of γ-silyl substituted cycloalkanoyl sulfoxides: the first examples and a new approach to 3-substituted cycloalk-2-enones

  摘要：

  The thermal decomposition of 3-(alpha-trimethylsilyl)alkyl substituted 2-(phenylsulfinyl)cycloalkanones occurs via the gamma-sila-Pummerer reaction, affording 3-substituted cycloalk-2-enones and unstable trimethylsilyl benzenesulfenate as an elimination by-product. The starting gamma-silyl substituted cycloalkanoyl sulfoxides were obtained through the conjugate addition reaction of nucleophilic reagents to 2-(phenylsulfinyl)cycloalk-2-enones. The tandem conjugate addition/gamma-sila-Pummerer reaction investigated here provides a new route to 3-substituted cycloalk-2-enones. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2014.04.128
• 作为产物：
  描述：

  2-(phenylthio)cyclopent-2-en-1-one 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 生成 2-(phenylsulfinyl)cyclopenten-2-one
  参考文献：
  名称：

  缺电子烯基亚砜的酰化：合成多取代酚和功能化碳环的多种转化

  摘要：

  开发了一种具有可用起始材料和温和条件的方案，用于通过缺电子烯基亚砜的酰化合成多取代酚和功能化碳环。研究了可能的机制。

  DOI：

  10.1055/a-2093-3233

文献信息

• Synthesis of 3-(Phosphorylmethyl)cycloalkenones by Forced Conjugate Addition of α-Phosphonate Carbanions to Cyclic Enones
  作者：Marian Mikolajczyk、Wieslawa Perlikowska

  DOI：10.1055/s-2007-965982

  日期：2007.4

  group giving 1,2-adducts. When complexes of cycloalkenones with aluminum tris(2,6-diphenylphenoxide) were used for this reaction, regioselective 1,4-addition was observed. Upon oxidation the thus-formed 1,4-adducts gave the corresponding 3-(phosphorylmethyl)cycloalk-2-enones. An alternative approach to the latter compounds involved 1,4-addition of diethyl lithiomethylphosphonate to 2-sulfinylcycloalk-2-enones

  发现环烯酮与 α-锂化二乙基（苯基硒基）甲基膦酸酯优先或仅在羰基处反应，产生 1,2-加合物。当环烯酮与三(2,6-二苯基苯氧基)铝的配合物用于该反应时，观察到区域选择性1,4-加成。如此形成的1，4-加合物在氧化后得到相应的3-（磷酰基甲基）环烷-2-烯酮。后一种化合物的另一种方法涉及将锂硫甲基膦酸二乙酯 1,4-加成到 2-亚磺酰基环烷-2-烯酮上，然后消除亚砜。
• An Efficient Synthesis of <i>p</i><i>eri</i>-Hydroxy Aromatic Compounds via a Strong-Base-Induced [4+2] Cycloaddition of Homophthalic Anhydrides with Enolizable Enones
  作者：Kiyosei Iio、Namakkal G. Ramesh、Akiko Okajima、Kazuhiro Higuchi、Hiromichi Fujioka、Shuji Akai、Yasuyuki Kita

  DOI：10.1021/jo990649q

  日期：2000.1.1

  An efficient synthesis of peri-hydroxy aromatic compounds has been accomplished via a strong-base-induced [4+2] cycloaddition of homophthalic anhydrides with alpha-sulfinyl-substituted derivatives of enolizable enones. The unsubstituted enones did not undergo an efficient [4+2] cycloaddition reaction with homophthalic anhydrides, presumably due to their enolization under the basic reaction conditions

  高羟基芳族化合物的有效合成已通过高碱诱导的高邻苯二甲酸酐与可烯醇化的烯酮的α-亚磺酰基取代的衍生物的[4 + 2]环加成反应完成。未取代的烯酮与高邻苯二甲酸酐未进行有效的[4 + 2]环加成反应，可能是由于它们在碱性反应条件下被烯醇化。亚磺酰基不仅促进环加成反应，而且在反应条件下进行原位消除，从而一步得到环羟基芳族化合物。描述了该方法在合成抗肿瘤抗生素腓特烈霉素A的关键中间体中的应用。还讨论了各种2-取代的环戊烯酮的PM3计算以及环加成的机理。
• A strong-base induced [4+2] cycloaddition of homophthalic anhydrides with enolizable enones: a direct and efficient synthesis of peri-hydroxy aromatic compounds
  作者：Namakkal G. Ramesh、Kiyosei Iio、Akiko Okajima、Shuji Akai、Yasuyuki Kita

  DOI：10.1039/a807095d

  日期：——

  A direct and efficient synthesis of peri-hydroxy aromatic compounds via a strong-base induced [4+2] cycloaddition of homophthalic anhydrides with α-phenylsulfinyl enolizable enones has been accomplished.

  通过强碱诱导均苯二甲酸酐与α-苯亚磺酰基可烯化烯酮的[4+2]环加成，直接高效地合成了近羟基芳香化合物。
• Preparation of New Chiral Building Blocks by a Mukaiyama–Michael Reaction of 2-(Phenylsulfonyl)cyclopent-2-en-1-one
  作者：Masahisa Nakada、Ryoji Sugiyama

  DOI：10.1055/a-2030-7082

  日期：——

  proceeds in 77% yield with a dr of 22:1 is also described. Because both enantiomers of the ligand for this Mukaiyama–Michael reaction are available, a method for the synthesis of all four stereoisomers of the product as useful chiral building blocks has been established.

  描述了使用硫代丙酸叔丁酯的烯醇硅烷进行 2-(苯磺酰基)环戊-2-en-1-one 的高度对映和非对映选择性 Mukaiyama-Michael 反应。在化学计量条件下，产物的产率为 87%，dr 为 27:1，ee 为 91%，而在催化条件下，产率、dr 和 ee 分别为 89%、49:1 和 88% ee。还描述了 Mukaiyama–Michael 反应产物的高度立体选择性差向异构化，其产率为 77%，dr 为 22:1。由于该 Mukaiyama–Michael 反应的配体的两种对映异构体都可用，因此已经建立了一种合成该产物的所有四种立体异构体作为有用的手性结构单元的方法。
• Cyclopentannulations leading to the synthesis of bicyclic conjugated enediones.
  作者：Tamar Yechezkel、Eugene Ghera、Daryl Ostercamp、Alfred Hassner

  DOI：10.1021/jo00121a035

  日期：1995.8

  Base-induced reactions of 1-(phenylsulfonyl)-2-methylene-3-bromopropane (4) with 2-(phenylsulfonyl)-2-cycloalkenones 8a-d were investigated with the ultimate purpose to develop a route leading to bicyclic conjugated enediones. Low-temperature, fast-quenched reactions led generally to open-chain adducts, while increase of temperature and addition of HMPA resulted in subsequent ring closure by a tandem Michael-S(N)2 process. The stereochemical features of the bicyclo[3.3.0]octanes 11 and 12, bicyclo[4.3.0]nonanes 18 and 19, bicyclo[5.3.0]decanes 22 and 23, and bicyclo[6.3.0]-undecanes 26-28 thus obtained have been determined. Ozonolysis and silica-induced elimination of the tertiary phenylsulfonyl group converted stereoselectively the above products into the desired enediones: pentalenedione 29, indenedione 30, azulenedione 32 and cyclopentacyclooctenedione 33, respectively.