trimethyl-[(Z)-2,2,5,6,6-pentamethylhept-3-en-3-yl]oxysilane | 173343-25-4

• 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: trimethyl-[(Z)-2,2,5,6,6-pentamethylhept-3-en-3-yl]oxysilane
• CAS: 173343-25-4
• 化学式: C₁₅H₃₂OSi
• 分子量: 256.504
• InChiKey: YSAUSLPLEIHMQS-QBFSEMIESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.45
• 重原子数：
  17.0
• 可旋转键数：
  3.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  苯甲醛 、 trimethyl-[(Z)-2,2,5,6,6-pentamethylhept-3-en-3-yl]oxysilane 以 苯 为溶剂， 以58%的产率得到(2RS,3RS,4SR,1'RS)-3-(1,1-dimethylethyl)-2-phenyl-4-(1,2,2-trimethylpropyl)-3-[(trimethylsilyl)oxy]oxetane
  参考文献：
  名称：

  1,3-Allylic Strain as a Control Element in the Paternò−Büchi Reaction of Chiral Silyl Enol Ethers:  Synthesis of Diastereomerically Pure Oxetanes Containing Four Contiguous Stereogenic Centers

  摘要：

  The facial diastereoselectivity in the Patemo-Buchi reaction of chiral silyl enol ethers and benzaldehyde was studied. The substituents (R(S), R(L)) at the stereogenic carbon atom (-C*HR(S)R(L)) attached to the beta-position of the silyl enol ether were varied in order to evaluate the influence of steric bulk and electronic effects. The combined yields for the two diastereomeric 3-(silyloxy)oxetanes a and b. range between 44% and 76%. In accordance with the 1,3-allylic strain model the facial diastereoselectivity (diastereomeric ratio (dr) = alb) was best with large(R(L) = t-Bu, SiMe(2)Ph) and polar (R(L) = OMe) substituents at the gamma-position of the silyl enol ether (dr up to >95/5). Two regioselective ring opening reactions were applied to the product oxetanes 29a, 50, and 51. They furnished diastereomerically pure diols (52, 53) and triols (31) in excellent yields.

  DOI：

  10.1021/ja963827v
• 作为产物：
  描述：

  三甲基氯硅烷 、 2,2,5,6,6-pentamethyl-heptan-3-one 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.0h， 生成 trimethyl-[(Z)-2,2,5,6,6-pentamethylhept-3-en-3-yl]oxysilane
  参考文献：
  名称：

  1,3-Allylic Strain as a Control Element in the Paternò−Büchi Reaction of Chiral Silyl Enol Ethers:  Synthesis of Diastereomerically Pure Oxetanes Containing Four Contiguous Stereogenic Centers

  摘要：

  The facial diastereoselectivity in the Patemo-Buchi reaction of chiral silyl enol ethers and benzaldehyde was studied. The substituents (R(S), R(L)) at the stereogenic carbon atom (-C*HR(S)R(L)) attached to the beta-position of the silyl enol ether were varied in order to evaluate the influence of steric bulk and electronic effects. The combined yields for the two diastereomeric 3-(silyloxy)oxetanes a and b. range between 44% and 76%. In accordance with the 1,3-allylic strain model the facial diastereoselectivity (diastereomeric ratio (dr) = alb) was best with large(R(L) = t-Bu, SiMe(2)Ph) and polar (R(L) = OMe) substituents at the gamma-position of the silyl enol ether (dr up to >95/5). Two regioselective ring opening reactions were applied to the product oxetanes 29a, 50, and 51. They furnished diastereomerically pure diols (52, 53) and triols (31) in excellent yields.

  DOI：

  10.1021/ja963827v

文献信息

• Bach, Thorsten; Joedicke, Kai; Kather, Kristian, Angewandte Chemie, 1995, vol. 107, # 20, p. 2455 - 2457
  作者：Bach, Thorsten、Joedicke, Kai、Kather, Kristian、Hecht, Juergen

  DOI：——

  日期：——