1-oxa-3-phenylseleno-2-(p-toluenesulfonyl)-2,5-cyclohexadiene

• 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-oxa-3-phenylseleno-2-(p-toluenesulfonyl)-2,5-cyclohexadiene
• 英文别名: 2-(4-methylphenyl)sulfonyl-3-phenylselanyl-4H-pyran
• 化学式: C₁₈H₁₆O₃SSe
• 分子量: 391.349
• InChiKey: APJKFEKJDKSREW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  51.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  1-phenylseleno-2-(p-toluenesulfonyl)ethyne 、 丙烯醛 反应 72.0h， 以38%的产率得到1-oxa-3-phenylseleno-2-(p-toluenesulfonyl)-2,5-cyclohexadiene
  参考文献：
  名称：

  Cycloaddition Reactions of 1-Phenylseleno-2-(p-toluenesulfonyl)ethyne

  摘要：

  1-Phenylseleno-2-(p-toluenesulfonyl)ethyne (1) is an effective dienophile and dipolarophile. It underwent facile Diels-Alder reactions with a variety of dienes to afford vicinal sulfone- and selenide-functionalized 1,4-cyclohexadienes. Unexpected regiochemistry that is the opposite of what is obtained with simple acetylenic sulfones was observed with several unsymmetrical dienes containing methyl or methoxy substituents at the 1- or 2-position. Acetylene 1 reacted with (trimethylsilyl)methyl azide, diazomethane, and 2,4,6-trimethylbenzonitrile N-oxide via 1,3-dipolar cycloadditions to afford the corresponding triazole, 1,2-diazole, and isoxazole products. It also underwent an ene reaction with beta-pinene that showed anomalous regiochemistry compared to other acetylenic sulfones. The Diels-Alder cycloadducts obtained from the reaction of 1 with 2,3-dimethyl-1,3,butadiene and 1,3-cyclohexadiene were readily converted into the corresponding beta-keto sulfones and ketones, thus rendering 1 as the synthetic equivalent of p-toluenesulfonylketene and ketene, respectively. Base-catalyzed elimination of TsOH from the Diels-Alder cycloadduct obtained with 2,3-dimethyl-1,3-butadiene afforded the corresponding aryl phenyl selenide, while the adduct from piperylene underwent oxidation to its selenoxide, followed by a Pummerer-type reaction to produce 2-(phenylseleno)-3-(p-toluenesulfonyl)toluene. The reaction of the bicyclic Diels-Alder product obtained from 1,3-cyclohexadiene with MeCu(SePh)Li resulted in substitution of the phenylseleno moiety by a methyl group, whereas similar treatment, of the monocyclic adduct derived from piperylene effected elimination of PhSeH and aromatization.

  DOI：

  10.1021/jo990730t

文献信息

• Cycloaddition Reactions of 1-Phenylseleno-2-(<i>p</i>-toluenesulfonyl)ethyne
  作者：Thomas G. Back、Richard J. Bethell、Masood Parvez、Jerry A. Taylor、Daniel Wehrli

  DOI：10.1021/jo990730t

  日期：1999.10.1

  1-Phenylseleno-2-(p-toluenesulfonyl)ethyne (1) is an effective dienophile and dipolarophile. It underwent facile Diels-Alder reactions with a variety of dienes to afford vicinal sulfone- and selenide-functionalized 1,4-cyclohexadienes. Unexpected regiochemistry that is the opposite of what is obtained with simple acetylenic sulfones was observed with several unsymmetrical dienes containing methyl or methoxy substituents at the 1- or 2-position. Acetylene 1 reacted with (trimethylsilyl)methyl azide, diazomethane, and 2,4,6-trimethylbenzonitrile N-oxide via 1,3-dipolar cycloadditions to afford the corresponding triazole, 1,2-diazole, and isoxazole products. It also underwent an ene reaction with beta-pinene that showed anomalous regiochemistry compared to other acetylenic sulfones. The Diels-Alder cycloadducts obtained from the reaction of 1 with 2,3-dimethyl-1,3,butadiene and 1,3-cyclohexadiene were readily converted into the corresponding beta-keto sulfones and ketones, thus rendering 1 as the synthetic equivalent of p-toluenesulfonylketene and ketene, respectively. Base-catalyzed elimination of TsOH from the Diels-Alder cycloadduct obtained with 2,3-dimethyl-1,3-butadiene afforded the corresponding aryl phenyl selenide, while the adduct from piperylene underwent oxidation to its selenoxide, followed by a Pummerer-type reaction to produce 2-(phenylseleno)-3-(p-toluenesulfonyl)toluene. The reaction of the bicyclic Diels-Alder product obtained from 1,3-cyclohexadiene with MeCu(SePh)Li resulted in substitution of the phenylseleno moiety by a methyl group, whereas similar treatment, of the monocyclic adduct derived from piperylene effected elimination of PhSeH and aromatization.