1-(2,4,10-trioxaadamant-3-yl)-3,4,4-trimethyl-1-[(trimethylsilyl)oxy]-1-pentene | 187811-66-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-(2,4,10-trioxaadamant-3-yl)-3,4,4-trimethyl-1-[(trimethylsilyl)oxy]-1-pentene
• 英文别名: trimethyl-[(Z)-3,4,4-trimethyl-1-(2,4,10-trioxatricyclo[3.3.1.13,7]decan-3-yl)pent-1-enoxy]silane
• CAS: 187811-66-1
• 化学式: C₁₈H₃₂O₄Si
• 分子量: 340.535
• InChiKey: HHGVYFDJTDQABD-PXNMLYILSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.42
• 重原子数：
  23.0
• 可旋转键数：
  4.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  36.92
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  苯甲醛 、 1-(2,4,10-trioxaadamant-3-yl)-3,4,4-trimethyl-1-[(trimethylsilyl)oxy]-1-pentene 以 苯 为溶剂， 以52%的产率得到2-phenyl-4-(1,2,2-trimethylpropyl)-3-(2,4,10-trioxaadamant-3-yl)-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：

  2,4,10-Trioxatricyclo[3.3.1.13,7]decane-3-carbonitrile 在 CuCN 作用下， 以 四氢呋喃 、 正戊烷 为溶剂， 反应 3.5h， 生成 1-(2,4,10-trioxaadamant-3-yl)-3,4,4-trimethyl-1-[(trimethylsilyl)oxy]-1-pentene
  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