μ-η2-[1-(3',4',5'-trimethoxyphenyl)-2-pentyne-4,4-dimethyl-1-ol]dicobalt hexacarbonyl | 1239695-05-6

• 英文名称: μ-η2-[1-(3',4',5'-trimethoxyphenyl)-2-pentyne-4,4-dimethyl-1-ol]dicobalt hexacarbonyl
• CAS: 1239695-05-6
• 化学式: C₂₂H₂₂Co₂O₁₀
• 分子量: 564.397
• InChiKey: YBGDMVGEEUIVAH-LHHHHTPCSA-N

反应信息

• 作为反应物：
  描述：

  μ-η2-[1-(3',4',5'-trimethoxyphenyl)-2-pentyne-4,4-dimethyl-1-ol]dicobalt hexacarbonyl 在 HBF₄*Me₂O 、 Zn 作用下， 以 diethyl ether 、 CH₂Cl₂ 为溶剂， 以69.5%的产率得到d,l-μ-η2-[5,6-di(3',4',5'-trimethoxyphenyl)-2,2,9,9-tetramethyl-3,7-decadiyne]bis(dicobalthexacarbonyl)
  参考文献：
  名称：

  1,3-Steric Induction in Intermolecular Radical Reactions Mediated by a Co₂(CO)₆−Metal Core

  摘要：

  Diastereoselectivity of propargyl coupling reactions can be controlled by using the bulkiness of a gamma-substituent as a stereochemical tool. This 1,3-steric induction was observed with gamma-t-Bu and gamma-Me3Si groups, both favoring a d,l-configuration of the head-to-head coupling products, 3,4-disubstituted 1,5-alkadiynes (d,l- 95-100%). X-ray crystallography analysis suggests that the most favorable orientation of converging propargyl radicals is the one in which the bulky gamma-substituents are positioned anti to each other. Overall, the synthetic strategy of employing a Me3Si auxiliary group involves five steps and affords, with 28-33% overall yields, pure d,l-3,4-diaryl-1,5-hexadiynes, otherwise hardly accessible.

  DOI：

  10.1021/om100472y
• 作为产物：
  描述：

  dicobalt octacarbonyl 、 3,3-二甲基-1-丁炔 、 3,4,5-三甲氧基苯甲醛 在 n-BuLi 作用下， 以 tetrahydrofuran 、 diethyl ether 为溶剂， 以21.2%的产率得到μ-η2-[1-(3',4',5'-trimethoxyphenyl)-2-pentyne-4,4-dimethyl-1-ol]dicobalt hexacarbonyl
  参考文献：
  名称：

  1,3-Steric Induction in Intermolecular Radical Reactions Mediated by a Co₂(CO)₆−Metal Core

  摘要：

  Diastereoselectivity of propargyl coupling reactions can be controlled by using the bulkiness of a gamma-substituent as a stereochemical tool. This 1,3-steric induction was observed with gamma-t-Bu and gamma-Me3Si groups, both favoring a d,l-configuration of the head-to-head coupling products, 3,4-disubstituted 1,5-alkadiynes (d,l- 95-100%). X-ray crystallography analysis suggests that the most favorable orientation of converging propargyl radicals is the one in which the bulky gamma-substituents are positioned anti to each other. Overall, the synthetic strategy of employing a Me3Si auxiliary group involves five steps and affords, with 28-33% overall yields, pure d,l-3,4-diaryl-1,5-hexadiynes, otherwise hardly accessible.

  DOI：

  10.1021/om100472y