(3S,4S)-3,4-bis(tert-butyldimethylsiloxy)oct-1-en-7-yne | 249603-92-7

• 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: (3S,4S)-3,4-bis(tert-butyldimethylsiloxy)oct-1-en-7-yne
• 英文别名: tert-butyl-[(3S,4S)-3-[tert-butyl(dimethyl)silyl]oxyoct-1-en-7-yn-4-yl]oxy-dimethylsilane
• CAS: 249603-92-7
• 化学式: C₂₀H₄₀O₂Si₂
• 分子量: 368.707
• InChiKey: QRJRGDLKULNIBN-ROUUACIJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.37
• 重原子数：
  24
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 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：

  (3S,4S)-3,4-bis(tert-butyldimethylsiloxy)oct-1-en-7-yne 在 二氯二茂锆 、 叔丁基锂 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 正己烷 、 正戊烷 为溶剂， 反应 1.83h， 生成
  参考文献：
  名称：

  A synthetic approach to palmerolides via Negishi cross coupling. The challenge of the C15–C16 bond formation

  摘要：

  The esterification of fragment C1-C8 (2) with fragment C16-C23 (3) to give iodo derivative 4, followed by a Pd-catalysed coupling with a C9-C15 fragment (7 or 8), may provide a common precursor of most palmerolides. Ligands and reaction conditions were exhaustively examined to perform the C15-C16 bond formation via Negishi reaction. With simple models, pre-activated Pd-Xantphos and Pd-DPEphos complexes were the most efficient catalysts at RT. Zincation of the C9-C15 fragment (8) and cross coupling with 4 required 3 equiv of t-BuLi, 10 mol % of Pd-Xantphos and 60 degrees C. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2014.06.066
• 作为产物：
  描述：

  ((4S,5S)-2,2-dimethyl-5-vinyl-1,3-dioxolan-4-yl)methanol 在 咪唑 、 copper(l) iodide 、 potassium carbonate 、 对甲苯磺酸 、 三乙胺 作用下， 以 甲醇 、 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 31.17h， 生成 (3S,4S)-3,4-bis(tert-butyldimethylsiloxy)oct-1-en-7-yne
  参考文献：
  名称：

  Stereocomplementary Construction of Optically Active Bicyclo[4.3.0]nonenone Derivatives

  摘要：

  Treatment of (5S,6S)-5,6-bis(tert-butyldimethylsiloxy)-8-(substituted)oct-1-en-7-yne derivatives, prepared from diethyl L-tartrate, with Co-2(CO)(8) afforded the corresponding cobalt-complexed enynes, which were subsequently exposed to the typical Pauson-Khand conditions to furnish highly stereoselectively or exclusively (2S,3S,6S)-2,3-bis(tert-butyldimetbylsiloxy)-9-(substituted)bicyclo[4.3.0]non-1(9)-en-8-ones. On the other hand, (3S,4S)-1-(substituted)oct-7-en-1-yne-3,4-diol congeners produced, on exposure to the Pauson-Khand conditions, (2S,3S,6R)-2,3-dihydroxy-9-(substituted) bicyclo[4.3.0]-non-1(9)-en-8-one derivatives in a highly stereoselective manner. The newly developed procedure has been shown to be useful for construction of the 2,3-bis(oxygenated)-7-(substituted)-bicyclo[4.3.0]non-6-en-8-one framework in a stereocomplementary as well as stereoselective fashion.

  DOI：

  10.1021/jo990819z