endo-2-Fluoro-endo-5-(methylthio)-9-oxabicyclo<4.2.1>nonane | 130516-73-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环己烷
• 英文名称: endo-2-Fluoro-endo-5-(methylthio)-9-oxabicyclo<4.2.1>nonane
• 英文别名: (1R,2R,5S,6S)-2-fluoro-5-methylsulfanyl-9-oxabicyclo[4.2.1]nonane
• CAS: 130516-73-3
• 化学式: C₉H₁₅FOS
• 分子量: 190.282
• InChiKey: NZJATCHUMOOKEL-HXFLIBJXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  34.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  Trans-2-fluorocyclooct-5-en-1-ol 、 dimethyl(methylthio)sulfonium tetrafluoroborate 以 二氯甲烷 为溶剂， 以8%的产率得到endo-2-Fluoro-endo-5-(methylthio)-9-oxabicyclo<4.2.1>nonane
  参考文献：
  名称：

  Synthesis of fluoroalkyl methyl thioethers by formal addition of methanesulfenyl fluoride to alkenes

  摘要：

  The electrophilic anti-1,2-addition of the elements of methanesulfenyl fluoride to carbon-carbon double bonds by a one-pot reaction of dimethyl(methylthio)sulfonium tetrafluoroborate and triethylamine trishydrofluoride with various types of alkenes is used for the synthesis of beta-fluoroalkyl methyl thioethers. This reaction is stereospecific: starting from cis-cycloalkenes (1) trans-1-fluoro-2-(methylthio)cycloalkanes (2) are formed, while trans-cyclododecene (3) gives the cis product 4 everytime in good yields. With unsymmetrical alkenes these reactions proceed regioselectively to produce Markovnikov-oriented fluoro thioethers. With 2,6-norbornadiene (26) exclusive exo attack on one double bond and subsequent transannular participation of the second pi-bond gives rise to two isomeric 3,5-disubstituted nortricyclanes, 28 and 29, while starting from the medium-sized cis,cis-1,5-cyclooctadiene (10) no transannular pi-participation is observed: the trans-1,2-addition product to one of the two double bonds in 11 is isolated. In contrast, in the reaction of the monoepoxide 30 of this diene in addition to the simple 1,2-adduct 31 a transannular oxygen participation occurs producing three oxa bicyclic compounds 32-34. The oxidation of 1-fluoro-2-(methylthio)cyclooctane (2a) by sodium periodate yields the expected mixture of two diastereomeric 1-fluoro-2-(methylsulfinyl)cyclooctanes (36) which on pyrolysis give 3-fluorocyclooctene (37).

  DOI：

  10.1021/jo00028a056

文献信息

• Synthesis of fluoroalkyl methyl thioethers by formal addition of methanesulfenyl fluoride to alkenes
  作者：Gunter Haufe、Gerard Alvernhe、Daniel Anker、Andre Laurent、Christine Saluzzo

  DOI：10.1021/jo00028a056

  日期：1992.1

  The electrophilic anti-1,2-addition of the elements of methanesulfenyl fluoride to carbon-carbon double bonds by a one-pot reaction of dimethyl(methylthio)sulfonium tetrafluoroborate and triethylamine trishydrofluoride with various types of alkenes is used for the synthesis of beta-fluoroalkyl methyl thioethers. This reaction is stereospecific: starting from cis-cycloalkenes (1) trans-1-fluoro-2-(methylthio)cycloalkanes (2) are formed, while trans-cyclododecene (3) gives the cis product 4 everytime in good yields. With unsymmetrical alkenes these reactions proceed regioselectively to produce Markovnikov-oriented fluoro thioethers. With 2,6-norbornadiene (26) exclusive exo attack on one double bond and subsequent transannular participation of the second pi-bond gives rise to two isomeric 3,5-disubstituted nortricyclanes, 28 and 29, while starting from the medium-sized cis,cis-1,5-cyclooctadiene (10) no transannular pi-participation is observed: the trans-1,2-addition product to one of the two double bonds in 11 is isolated. In contrast, in the reaction of the monoepoxide 30 of this diene in addition to the simple 1,2-adduct 31 a transannular oxygen participation occurs producing three oxa bicyclic compounds 32-34. The oxidation of 1-fluoro-2-(methylthio)cyclooctane (2a) by sodium periodate yields the expected mixture of two diastereomeric 1-fluoro-2-(methylsulfinyl)cyclooctanes (36) which on pyrolysis give 3-fluorocyclooctene (37).