(E)-3,8-Bis-(tert-butyl-dimethyl-silanyloxy)-4,4-dimethyl-1-trimethylsilanyl-oct-6-en-1-yne | 284034-59-9

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (E)-3,8-Bis-(tert-butyl-dimethyl-silanyloxy)-4,4-dimethyl-1-trimethylsilanyl-oct-6-en-1-yne
• 英文别名: [(E)-3,8-bis[[tert-butyl(dimethyl)silyl]oxy]-4,4-dimethyloct-6-en-1-ynyl]-trimethylsilane
• CAS: 284034-59-9
• 化学式: C₂₅H₅₂O₂Si₃
• 分子量: 468.943
• InChiKey: BOWVMYJENSJJCK-WUKNDPDISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.25
• 重原子数：
  30
• 可旋转键数：
  11
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.84
• 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：

  (E)-3,8-Bis-(tert-butyl-dimethyl-silanyloxy)-4,4-dimethyl-1-trimethylsilanyl-oct-6-en-1-yne 在 dicobalt octacarbonyl 作用下， 以 甲苯 为溶剂， 反应 12.0h， 以71%的产率得到(3R,5S)-3-(tert-Butyl-dimethyl-silanyloxy)-5-[(E)-3-(tert-butyl-dimethyl-silanyloxy)-propenyl]-4,4-dimethyl-1-trimethylsilanyl-cyclopentene
  参考文献：
  名称：

  Diastereoselective Formation of 5-Vinylcyclopentenes from 1,6-Enynes:  Cobalt-Mediated C−H Allylic Activation and Formal 5-Endo-Dig Cyclization

  摘要：

  [GRAPHICS]A novel intramolecular cyclization reaction mediated by dicobalt octacarbonyl (Co-2(CO)(8)) is reported. Thermolysis in an argon atmosphere transforms the cobalt complex of 1-trimethyisilyl-6-hepten-1-ynes into 1-trimethylsilyl-5-vinylcyclopentenes in good yield and in a highly diastereoselective manner. This formal 5-endo-dig cyclization is proposed to proceed via an allylic C-H oxidative addition.

  DOI：

  10.1021/ol005928a
• 作为产物：
  描述：

  3,3-dimethyl-4-((dimethylethyl)dimethylsilyloxy)-6-trimethylsilyl-5-hexyn-1-al 在 咪唑 、 sodium hydride 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 17.0h， 生成 (E)-3,8-Bis-(tert-butyl-dimethyl-silanyloxy)-4,4-dimethyl-1-trimethylsilanyl-oct-6-en-1-yne
  参考文献：
  名称：

  Diastereoselective Formation of 5-Vinylcyclopentenes from 1,6-Enynes:  Cobalt-Mediated C−H Allylic Activation and Formal 5-Endo-Dig Cyclization

  摘要：

  [GRAPHICS]A novel intramolecular cyclization reaction mediated by dicobalt octacarbonyl (Co-2(CO)(8)) is reported. Thermolysis in an argon atmosphere transforms the cobalt complex of 1-trimethyisilyl-6-hepten-1-ynes into 1-trimethylsilyl-5-vinylcyclopentenes in good yield and in a highly diastereoselective manner. This formal 5-endo-dig cyclization is proposed to proceed via an allylic C-H oxidative addition.

  DOI：

  10.1021/ol005928a

文献信息

• Cobalt-Catalyzed Cycloisomerization of 1,6-Enynes and Allyl Propargyl Ethers
  作者：Alain Ajamian、James L. Gleason

  DOI：10.1021/ol034541f

  日期：2003.7.1

  6-Enynes and allyl propargyl ethers undergo a cobalt-catalyzed formal 5-endo-dig cyclization to form vinyl cyclopentenes and dihydrofurans, respectively. The use of equimolar amounts of dicobalt octacarbonyl and trimethyl phosphite affords optimum yields and improved selectivity for cycloisomerization vs alkene isomerization.

  [反应：见正文] 1，6-炔烃和烯丙基炔丙基醚经过钴催化的5-内位-dig环化反应分别形成乙烯基环戊烯和二氢呋喃。等摩尔量的八羰基二钴二亚磷酸酯和亚磷酸三甲酯可提供最佳收率，并提高环异构化与烯烃异构化的选择性。