(Z)-5-(tert-butyldiphenylsilyl)oxy-3-methyl-1-trimethylsilyl-3-penten-1-yne | 848691-91-8

• 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: (Z)-5-(tert-butyldiphenylsilyl)oxy-3-methyl-1-trimethylsilyl-3-penten-1-yne
• 英文别名: tert-butyl-[(Z)-3-methyl-5-trimethylsilylpent-2-en-4-ynoxy]-diphenylsilane
• CAS: 848691-91-8
• 化学式: C₂₅H₃₄OSi₂
• 分子量: 406.715
• InChiKey: UORAVBHPBRGWRF-PYCFMQQDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.39
• 重原子数：
  28
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (Z)-5-(tert-butyldiphenylsilyl)oxy-3-methyl-1-trimethylsilyl-3-penten-1-yne 在 锂硼氢 、 cerium(III) chloride 、 (Sia)2BH 、 potassium carbonate 、 戴斯-马丁氧化剂 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 丙酮 为溶剂， 反应 28.0h， 生成 (2E,5Z)-(1R)-7-(tert-butyldiphenylsilyl)oxy-1-{(4R,5S)-2,2-dimethyl-5-[2-(4-methoxybenzyloxy)ethyl]-[1,3]-dioxolan-4-yl}-5-methyl-hepta-2,5-dien-1-ol
  参考文献：
  名称：

  Stereoselective preparation of trisubstituted (Z)-alkenes; synthesis of the C17–C27 fragment of (−)-laulimalide

  摘要：

  A Ni-catalyzed cross-coupling reaction of (Z)-5-(tert-butyldiphenylsilyl)oxy-3-bromo-1-trimethylsilyl-3-penten-1-yne (1) with alkyl Grignard reagent gives (Z)-3-alkyl-5-(tert-butyldiphenylsilyl)oxy-1-trimethylsilyl-3-penten-1-ynes (2) stereospecifically in good yields. The (Z)-enyne 2a is transformed in four steps to (Z)-3-methyl-5-silyloxy-3-pentenaI (3), which is coupled with ketophosphonate 4 to give enone 13. The eta-hydroxyallyl methanesulfonate derived from 13 is cyclized to 3,6-dihydro[2H]pyran by an intramolecular SN2' reaction stereoselectively, furnishing a C17-C27 carbon unit of (-)-laulimalide. (C) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.01.002
• 作为产物：
  描述：

  甲基溴化镁 、 3-bromo-1-(tert-butyldiphenylsilyl)oxy-5-trimethylsilyl-2-penten-4-yne 在 1,3-bis[(diphenylphosphino)propane]dichloronickel(II) 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以84%的产率得到(Z)-5-(tert-butyldiphenylsilyl)oxy-3-methyl-1-trimethylsilyl-3-penten-1-yne
  参考文献：
  名称：

  Stereoselective preparation of trisubstituted (Z)-alkenes; synthesis of the C17–C27 fragment of (−)-laulimalide

  摘要：

  A Ni-catalyzed cross-coupling reaction of (Z)-5-(tert-butyldiphenylsilyl)oxy-3-bromo-1-trimethylsilyl-3-penten-1-yne (1) with alkyl Grignard reagent gives (Z)-3-alkyl-5-(tert-butyldiphenylsilyl)oxy-1-trimethylsilyl-3-penten-1-ynes (2) stereospecifically in good yields. The (Z)-enyne 2a is transformed in four steps to (Z)-3-methyl-5-silyloxy-3-pentenaI (3), which is coupled with ketophosphonate 4 to give enone 13. The eta-hydroxyallyl methanesulfonate derived from 13 is cyclized to 3,6-dihydro[2H]pyran by an intramolecular SN2' reaction stereoselectively, furnishing a C17-C27 carbon unit of (-)-laulimalide. (C) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.01.002