<3-(phenylsulfonyl)-3-cyanopropyl>oxirane | 155354-50-0

• 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: <3-(phenylsulfonyl)-3-cyanopropyl>oxirane
• 英文别名: 2-(Benzenesulfonyl)-4-(oxiran-2-yl)butanenitrile
• CAS: 155354-50-0
• 化学式: C₁₂H₁₃NO₃S
• 分子量: 251.306
• InChiKey: UNNZNDMBKROLSQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  78.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  <3-(phenylsulfonyl)-3-cyanopropyl>oxirane 以90%的产率得到
  参考文献：
  名称：

  Benedetti Fabio, Berti Federico, Fabrisain Silvio, Gianferrara Teresa, J. Org. Chem, 59 (1994) N 6, S 1518-1524

  摘要：

  DOI：
• 作为产物：
  描述：

  5-(phenylsulfonyl)-5-cyano-1-pentene 在 间氯过氧苯甲酸 作用下， 以 氯仿 为溶剂， 生成 <3-(phenylsulfonyl)-3-cyanopropyl>oxirane
  参考文献：
  名称：

  Intramolecular Ring Opening of Epoxides by Bis-Activated Carbanions. The Influence of Ring Size on Reactivity and Selectivity

  摘要：

  A quantitative study on the effect of ring size in the intramolecular ring opening of epoxides by carbanions is described. Two series of substrates were examined: alpha,alpha-bis-sulfonyl omega-epoxides 1 and alpha-cyano-alpha-sulfonyl omega-epoxides 2; in each series the carbanion is tethered to the epoxide by a chain of variable length from one to four methylene groups. The nucleophile can attack either electrophilic position of the oxirane ring, or both; exo ring opening of cyano sulfonyl epoxides 2 is followed by a second cyclization leading eventually to bicyclic, fused gamma-lactones. Both series of epoxides show the same trend of reactivity as a function of ring size, in the formation of three- to seven-membered rings, with reactivity maxima corresponding to the formation of cyclopropane and cyclopentane derivatives. Unlike S(N)2 ring closure of omega-halogeno carbanions, cyclization to a five-membered ring is the fastest process in this case. The ratio k3/k5 between formation of three- and five-membered rings drops from over 100, in the S(N)2 cyclization of omega-iodo bis-sulfones, to less than 0.5, in the cyclization of omega-epoxy bis-sulfones 1. The difference is discussed in terms of trajectory of approach of the carbanion to the nucleophilic center. Cyclization of cyano sulfonyl epoxide 2a, in which the nucleophilic center and the epoxide are spaced by a single methylene group, is diastereoselective and leads to a bicyclic product with a cis fusion between the gamma-lactone and the cyclopropane ring.

  DOI：

  10.1021/jo00085a045

文献信息

• Benedetti Fabio, Berti Federico, Fabrisain Silvio, Gianferrara Teresa, J. Org. Chem, 59 (1994) N 6, S 1518-1524
  作者：Benedetti Fabio, Berti Federico, Fabrisain Silvio, Gianferrara Teresa

  DOI：——

  日期：——
• Intramolecular Ring Opening of Epoxides by Bis-Activated Carbanions. The Influence of Ring Size on Reactivity and Selectivity
  作者：Fabio Benedetti、Federico Berti、Silvio Fabrissin、Teresa Gianferrara

  DOI：10.1021/jo00085a045

  日期：1994.3

  A quantitative study on the effect of ring size in the intramolecular ring opening of epoxides by carbanions is described. Two series of substrates were examined: alpha,alpha-bis-sulfonyl omega-epoxides 1 and alpha-cyano-alpha-sulfonyl omega-epoxides 2; in each series the carbanion is tethered to the epoxide by a chain of variable length from one to four methylene groups. The nucleophile can attack either electrophilic position of the oxirane ring, or both; exo ring opening of cyano sulfonyl epoxides 2 is followed by a second cyclization leading eventually to bicyclic, fused gamma-lactones. Both series of epoxides show the same trend of reactivity as a function of ring size, in the formation of three- to seven-membered rings, with reactivity maxima corresponding to the formation of cyclopropane and cyclopentane derivatives. Unlike S(N)2 ring closure of omega-halogeno carbanions, cyclization to a five-membered ring is the fastest process in this case. The ratio k3/k5 between formation of three- and five-membered rings drops from over 100, in the S(N)2 cyclization of omega-iodo bis-sulfones, to less than 0.5, in the cyclization of omega-epoxy bis-sulfones 1. The difference is discussed in terms of trajectory of approach of the carbanion to the nucleophilic center. Cyclization of cyano sulfonyl epoxide 2a, in which the nucleophilic center and the epoxide are spaced by a single methylene group, is diastereoselective and leads to a bicyclic product with a cis fusion between the gamma-lactone and the cyclopropane ring.