7-methylene-5,9-dioxatrideca-2,11-diyne | 1015098-87-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 7-methylene-5,9-dioxatrideca-2,11-diyne
• 英文别名: 3-But-2-ynoxy-2-(but-2-ynoxymethyl)prop-1-ene
• CAS: 1015098-87-9
• 化学式: C₁₂H₁₆O₂
• 分子量: 192.258
• InChiKey: DAIKQMVSHIICCR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  7-methylene-5,9-dioxatrideca-2,11-diyne 在 bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 、 [2'-(diphenylphosphanyl)-[1,1'-binaphthalen]-2-yl]diphenylphosphane 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 6.0h， 以78%的产率得到7-methyl-6-methylene-3,10-dioxatricyclo[6.3.1.0^1,8]dodec-7-ene
  参考文献：
  名称：

  Enantioselective Syntheses of Various Chiral Multicyclic Compounds with Quaternary Carbon Stereocenters by Catalytic Intramolecular Cycloaddition

  摘要：

  The intramolecular cycloaddition of 1,n-diene-ynes (n = 4-6), where alkyne and alkene moieties are connected by a 1,1-disubstituted alkene, was examined using a chiral rhodium catalyst, and various types of cycloadducts with quaternary carbon stereocenter(s) were obtained in high to excellent enantiomeric excess. In the case of 1,4-diene-ynes, tricyclic, bicyclic, and spirocyclic compounds were obtained depending upon the substituents at the 2-position of the 1,4-diene moiety and those at their alkyne termini. On the other hand, 1,5- and 1,6-diene-ynes gave tricyclic and bicyclic compounds, which included medium-sized ring systems. The mechanistic considerations for different reaction pathways and the synthetic transformation of tricyclic products into functionalized spirocyclic compounds are also described. The reaction of enediynes, where two alkyne moieties are connected by a 1,1-disubstituted alkene, was also examined, and sterically strained tricyclic compounds with two carbon stereocenters were obtained.

  DOI：

  10.1021/ja0762083
• 作为产物：
  描述：

  2-亚甲基-1,3-丙二醇 、 1-溴-2-丁炔 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 生成 7-methylene-5,9-dioxatrideca-2,11-diyne
  参考文献：
  名称：

  Enantioselective Syntheses of Various Chiral Multicyclic Compounds with Quaternary Carbon Stereocenters by Catalytic Intramolecular Cycloaddition

  摘要：

  The intramolecular cycloaddition of 1,n-diene-ynes (n = 4-6), where alkyne and alkene moieties are connected by a 1,1-disubstituted alkene, was examined using a chiral rhodium catalyst, and various types of cycloadducts with quaternary carbon stereocenter(s) were obtained in high to excellent enantiomeric excess. In the case of 1,4-diene-ynes, tricyclic, bicyclic, and spirocyclic compounds were obtained depending upon the substituents at the 2-position of the 1,4-diene moiety and those at their alkyne termini. On the other hand, 1,5- and 1,6-diene-ynes gave tricyclic and bicyclic compounds, which included medium-sized ring systems. The mechanistic considerations for different reaction pathways and the synthetic transformation of tricyclic products into functionalized spirocyclic compounds are also described. The reaction of enediynes, where two alkyne moieties are connected by a 1,1-disubstituted alkene, was also examined, and sterically strained tricyclic compounds with two carbon stereocenters were obtained.

  DOI：

  10.1021/ja0762083