5-(phenylsulfonyl)-5,6-heptadien-2-one | 112841-23-3

• 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: 5-(phenylsulfonyl)-5,6-heptadien-2-one
• 英文别名: 3-(Phenylsulfonyl)-1,2-heptadien-6-one
• CAS: 112841-23-3
• 化学式: C₁₃H₁₄O₃S
• 分子量: 250.318
• InChiKey: XCNNWJLSDRPXIK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  59.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  phenylsulfonylpropa-1,2-diene 、 丁烯酮 在 sodium methylate 作用下， 以 四氢呋喃 为溶剂， 反应 14.0h， 以81%的产率得到5-(phenylsulfonyl)-5,6-heptadien-2-one
  参考文献：
  名称：

  [3 + 2] Cyclization-elimination route to cyclopentenyl sulfones using (phenylsulfonyl)-1,2-propadiene

  摘要：

  Treatment of (phenylsulfonyl)-1,2-propadiene (1) with bis(phenylsulfonyl)methane in the presence of sodium hydride affords 2,4,4-tris(phenylsulfonyl)-1-butene in 94% yield. Similar rearranged products were obtained using other soft nucleophiles and related allenes. The formation of these products involves addition of benzenesulfinate anion onto allene 1. The initially formed carbanion undergoes proton transfer with bis(phenylsulfonyl)methane followed by a S(N)2' reaction of the resulting anion with 2,3-bis(phenylsulfonyl)-1-propene. Supporting evidence for the proposed mechanism is provided by the observation that the reaction of dimethyl malonate with the activated allene in the presence of sodium benzenesulfinate gives mostly abnormal products. When allene 1 is allowed to react with olefins bearing an electron-withdrawing group in the presence of sodium benzenesulfinate, a substituted cyclopentenyl sulfone is formed. The reaction proceeds in a stepwise fashion by addition of the initially produced carbanion onto the activated pi-bond of the olefin followed by a 5-endo-trig cyclization and elimination of benzenesulfinate. This approach represents a mild and versatile anionic [3 + 2] route to five-membered unsaturated sulfones.

  DOI：

  10.1021/jo00022a032

文献信息

• Cyclization Reactions of 2,3-Bis(phenylsulfonyl)-1,3-butadiene with Various Carbanions. A [4 + 1] Anionic Annulation Approach to Phenylsulfonyl-Substituted Cyclopentenes
  作者：Albert Padwa、Michelle A. Filipkowski、Michael Meske、S. Shaun Murphree、Scott H. Watterson、Zhijie Ni

  DOI：10.1021/jo00082a015

  日期：1994.2

  2,3-Bis(phenylsulfonyl)-1,3-butadiene undergo es conjugate addition in the presence of carbanions giving rise to a variety of unsaturated sulfones. Reaction with lithium enolates proceeds via an allylic anionic intermediate which undergoes a subsequent elimination of phenylsulfinate anion to produce an allene. Generation of enolates from silyl enol ethers results in conjugate addition to the diene without subsequent elimination. Substituted cyclopentenyl sulfones are available via a [4 + 1] annulation reaction of the diene with various distabilized carbanions. The reaction involves a tandem addition-proton exchange-addition sequence. In the special case of 2,4-pentanedione, pyrans are formed, the isomeric identity of which depends upon the reaction conditions. 2-Alkylated 1,3-dicarbonyl compounds react with the activated diene to produce substituted allenes in high yield. Phenylsulfonyl alkenyl substituted allenes were conveniently prepared by a similar protocol and were found to serve as substrates for intramolecular [2 + 2] cycloaddition chemistry.
• Synthesis of cyclopentenyl sulfones via the [3 + 2] cyclization-elimination reaction of (phenylsulfonyl)allene
  作者：Albert. Padwa、Philip E. Yeske

  DOI：10.1021/ja00213a042

  日期：1988.3
• PADWA, ALBERT;YESKE, PHILIP E., J. AMER. CHEM. SOC., 110,(1988) N 5, 1617-1618
  作者：PADWA, ALBERT、YESKE, PHILIP E.

  DOI：——

  日期：——
• [3 + 2] Cyclization-elimination route to cyclopentenyl sulfones using (phenylsulfonyl)-1,2-propadiene
  作者：Albert Padwa、Philip E. Yeske

  DOI：10.1021/jo00022a032

  日期：1991.10

  Treatment of (phenylsulfonyl)-1,2-propadiene (1) with bis(phenylsulfonyl)methane in the presence of sodium hydride affords 2,4,4-tris(phenylsulfonyl)-1-butene in 94% yield. Similar rearranged products were obtained using other soft nucleophiles and related allenes. The formation of these products involves addition of benzenesulfinate anion onto allene 1. The initially formed carbanion undergoes proton transfer with bis(phenylsulfonyl)methane followed by a S(N)2' reaction of the resulting anion with 2,3-bis(phenylsulfonyl)-1-propene. Supporting evidence for the proposed mechanism is provided by the observation that the reaction of dimethyl malonate with the activated allene in the presence of sodium benzenesulfinate gives mostly abnormal products. When allene 1 is allowed to react with olefins bearing an electron-withdrawing group in the presence of sodium benzenesulfinate, a substituted cyclopentenyl sulfone is formed. The reaction proceeds in a stepwise fashion by addition of the initially produced carbanion onto the activated pi-bond of the olefin followed by a 5-endo-trig cyclization and elimination of benzenesulfinate. This approach represents a mild and versatile anionic [3 + 2] route to five-membered unsaturated sulfones.