3-(dimethylphenylsilyl)-1-(2-methyl-1,3-dioxolan-2-yl)-3-[(trimethylsilyl)oxy]-1-butene | 187811-69-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-(dimethylphenylsilyl)-1-(2-methyl-1,3-dioxolan-2-yl)-3-[(trimethylsilyl)oxy]-1-butene
• 英文别名: dimethyl-[(Z)-4-(2-methyl-1,3-dioxolan-2-yl)-4-trimethylsilyloxybut-3-en-2-yl]-phenylsilane
• CAS: 187811-69-4
• 化学式: C₁₉H₃₂O₃Si₂
• 分子量: 364.632
• InChiKey: IPBAJCVZKVAYOU-SDXDJHTJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.49
• 重原子数：
  24
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-(dimethylphenylsilyl)-1-(2-methyl-1,3-dioxolan-2-yl)-3-[(trimethylsilyl)oxy]-1-butene 在 四丁基氟化铵 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 3.0h， 生成 2-(2-methyl-1,3-dioxolan-2-yl)-1-phenyl-3-penten-1,2-diol
  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 、 dimethyl(phenyl)silyllithium 、 (E)-1-(2-methyl-1,3-dioxolan-2-yl)but-2-en-1-one 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 20.0h， 以86%的产率得到3-(dimethylphenylsilyl)-1-(2-methyl-1,3-dioxolan-2-yl)-3-[(trimethylsilyl)oxy]-1-butene
  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

• 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
  作者：Thorsten Bach、Kai Jödicke、Kristian Kather、Roland Fröhlich

  DOI：10.1021/ja963827v

  日期：1997.3.1

  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.