methyl 2-carbomethoxy-3-<(phenylsulfonyl)methyl>-3-butenoate | 112841-15-3

• 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: methyl 2-carbomethoxy-3-<(phenylsulfonyl)methyl>-3-butenoate
• 英文别名: Dimethyl [3-(benzenesulfonyl)prop-1-en-2-yl]propanedioate；dimethyl 2-[3-(benzenesulfonyl)prop-1-en-2-yl]propanedioate
• CAS: 112841-15-3
• 化学式: C₁₄H₁₆O₆S
• 分子量: 312.343
• InChiKey: DJRVVLYGVOTGLE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  21
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  95.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 2-carbomethoxy-3-<(phenylsulfonyl)methyl>-3-butenoate 在 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 生成 methyl 2-carbomethoxy-3-<(phenylsulfonyl)methyl>-2-butenoate
  参考文献：
  名称：

  Synthesis of cyclopentenyl sulfones via the [3 + 2] cyclization-elimination reaction of (phenylsulfonyl)allene

  摘要：

  DOI：

  10.1021/ja00213a042
• 作为产物：
  描述：

  phenylsulfonylpropa-1,2-diene 、 丙二酸二甲酯 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 18.0h， 以92%的产率得到methyl 2-carbomethoxy-3-<(phenylsulfonyl)methyl>-3-butenoate
  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

• 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.