1,6-Bis-dec-9-enyl-9-thia-bicyclo[4.2.1]nonane 9,9-dioxide | 264878-52-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻庚烷
• 英文名称: 1,6-Bis-dec-9-enyl-9-thia-bicyclo[4.2.1]nonane 9,9-dioxide
• 英文别名: 1,6-Bis(dec-9-enyl)-9lambda6-thiabicyclo[4.2.1]nonane 9,9-dioxide；1,6-bis(dec-9-enyl)-9λ6-thiabicyclo[4.2.1]nonane 9,9-dioxide
• CAS: 264878-52-6
• 化学式: C₂₈H₅₀O₂S
• 分子量: 450.77
• InChiKey: KILCHUAPLNICLP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.1
• 重原子数：
  31
• 可旋转键数：
  18
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  42.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,6-Bis-dec-9-enyl-9-thia-bicyclo[4.2.1]nonane 9,9-dioxide 在 Grubbs catalyst first generation 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以29%的产率得到
  参考文献：
  名称：

  Catalytic Ring-Closing Metathesis of Doubly Armed, Bridged Bicyclic Sulfones. Evaluation of Chain Length and Possible Intramolecular SO₂ Group Ligation to the Ruthenium Carbenoid

  摘要：

  Disubstituted bicyclic sulfones 3a-3d, which were prepared by the 2-fold alkylation of 1,6-dilithio-9-thiabicyclor[4.2.1]nonane dioxide, undergo ring-closing metathesis to give a select few of the possible dimers and trimers. Only in the case of 3d were monomeric end products formed. The pronounced diastereoselectivities observed, particularly with the two lowest homologues, are suggested to be kinetically favored because of the operation of internal ruthenium/sulfonyl oxygen coordination during generation of the first intermolecular double bond. This ligation appears to be an important component of the overall reaction in that it serves to maximize unfavorable nonbonded steric interactions when the sulfone bridges adopt a syn relationship. MM3 calculations indicate the anti sulfone dimersalso to be thermodynamically favored when n = 3. The preference for the anti sulfone arrangement appears to erode with an increase in the length of the tethers. Not unexpectedly, a ring size dependency is likely at play. The development of a ring-closing metathesis strategy for the incorporation of sulfone groups into stereochemically defined polybicyclic molecules has been realized.

  DOI：

  10.1021/ja9943849
• 作为产物：
  描述：

  9-Thiabicyclo<4.2.1>nonan-9,9-dioxid 、 10-iodo-1-decene 在 叔丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 4.67h， 以75%的产率得到1,6-Bis-dec-9-enyl-9-thia-bicyclo[4.2.1]nonane 9,9-dioxide
  参考文献：
  名称：

  Catalytic Ring-Closing Metathesis of Doubly Armed, Bridged Bicyclic Sulfones. Evaluation of Chain Length and Possible Intramolecular SO₂ Group Ligation to the Ruthenium Carbenoid

  摘要：

  Disubstituted bicyclic sulfones 3a-3d, which were prepared by the 2-fold alkylation of 1,6-dilithio-9-thiabicyclor[4.2.1]nonane dioxide, undergo ring-closing metathesis to give a select few of the possible dimers and trimers. Only in the case of 3d were monomeric end products formed. The pronounced diastereoselectivities observed, particularly with the two lowest homologues, are suggested to be kinetically favored because of the operation of internal ruthenium/sulfonyl oxygen coordination during generation of the first intermolecular double bond. This ligation appears to be an important component of the overall reaction in that it serves to maximize unfavorable nonbonded steric interactions when the sulfone bridges adopt a syn relationship. MM3 calculations indicate the anti sulfone dimersalso to be thermodynamically favored when n = 3. The preference for the anti sulfone arrangement appears to erode with an increase in the length of the tethers. Not unexpectedly, a ring size dependency is likely at play. The development of a ring-closing metathesis strategy for the incorporation of sulfone groups into stereochemically defined polybicyclic molecules has been realized.

  DOI：

  10.1021/ja9943849

文献信息

• Catalytic Ring-Closing Metathesis of Doubly Armed, Bridged Bicyclic Sulfones. Evaluation of Chain Length and Possible Intramolecular SO₂ Group Ligation to the Ruthenium Carbenoid
  作者：Leo A. Paquette、Fabrizio Fabris、Jinsung Tae、Judith C. Gallucci、John E. Hofferberth

  DOI：10.1021/ja9943849

  日期：2000.4.1

  Disubstituted bicyclic sulfones 3a-3d, which were prepared by the 2-fold alkylation of 1,6-dilithio-9-thiabicyclor[4.2.1]nonane dioxide, undergo ring-closing metathesis to give a select few of the possible dimers and trimers. Only in the case of 3d were monomeric end products formed. The pronounced diastereoselectivities observed, particularly with the two lowest homologues, are suggested to be kinetically favored because of the operation of internal ruthenium/sulfonyl oxygen coordination during generation of the first intermolecular double bond. This ligation appears to be an important component of the overall reaction in that it serves to maximize unfavorable nonbonded steric interactions when the sulfone bridges adopt a syn relationship. MM3 calculations indicate the anti sulfone dimersalso to be thermodynamically favored when n = 3. The preference for the anti sulfone arrangement appears to erode with an increase in the length of the tethers. Not unexpectedly, a ring size dependency is likely at play. The development of a ring-closing metathesis strategy for the incorporation of sulfone groups into stereochemically defined polybicyclic molecules has been realized.