1-(2,4,10-trioxaadamant-3-yl)-2-buten-1-one | 187811-65-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二恶烷
• 英文名称: 1-(2,4,10-trioxaadamant-3-yl)-2-buten-1-one
• 英文别名: (E)-1-(2,4,10-trioxatricyclo[3.3.1.13,7]decan-3-yl)but-2-en-1-one
• CAS: 187811-65-0
• 化学式: C₁₁H₁₄O₄
• 分子量: 210.23
• InChiKey: PVFBWWYMPQLPGN-NSCUHMNNSA-N

物化性质

• 沸点：
  310.7±42.0 °C(Predicted)
• 密度：
  1.272±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-(2,4,10-trioxaadamant-3-yl)-2-buten-1-one 在 CuCN 作用下， 以 四氢呋喃 、 正戊烷 、 苯 为溶剂， 反应 1.58h， 生成 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：

  (E)-1-propenylmagnesium bromide 、 2,4,10-Trioxatricyclo[3.3.1.13,7]decane-3-carbonitrile 以 四氢呋喃 为溶剂， 反应 1.92h， 以71%的产率得到1-(2,4,10-trioxaadamant-3-yl)-2-buten-1-one
  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