[(1S,3R,6S,8R)-4-methylidene-2-oxatricyclo[4.3.0.01,3]nonan-8-yl]oxy-tri(propan-2-yl)silane | 1374117-09-5

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: [(1S,3R,6S,8R)-4-methylidene-2-oxatricyclo[4.3.0.01,3]nonan-8-yl]oxy-tri(propan-2-yl)silane
• CAS: 1374117-09-5
• 化学式: C₁₈H₃₂O₂Si
• 分子量: 308.536
• InChiKey: ZVTLVTYSPXMHPC-MLHJIOFPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.05
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  21.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  [(1S,3R,6S,8R)-4-methylidene-2-oxatricyclo[4.3.0.01,3]nonan-8-yl]oxy-tri(propan-2-yl)silane 在 scandium tris(trifluoromethanesulfonate) 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以78%的产率得到
  参考文献：
  名称：

  A Tandem Cross-Metathesis/Semipinacol Rearrangement Reaction

  摘要：

  An efficient and (E)-selective synthesis of a 6-alkylidenebicyclo[3.2.1]octan-8-one has been developed. The key step is a tandem cross-metathesis/semipinacol rearrangement reaction, wherein the Hoveyda-Grubbs II catalyst, or more likely a derivative thereof, serves as the Lewis acid for the rearrangement. Despite the fact that both the starting alkene and the cross-metathesis product are viable rearrangement substrates, only the latter rearranges, suggesting that the Lewis acidic species is generated only after the cross-metathesis reaction is complete.

  DOI：

  10.1021/ol300691u
• 作为产物：
  描述：

  (R)-2-but-3-enyloxirane 在 2,6-二甲基吡啶 、 正丁基锂 、 dicobalt octacarbonyl 、 四甲基硫脲 、 双氧水 、 potassium carbonate 、 sodium hydroxide 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 正己烷 、 二氯甲烷 、 水 、 苯 为溶剂， -78.0~70.0 ℃ 、101.33 kPa 条件下， 反应 30.5h， 生成 [(1S,3R,6S,8R)-4-methylidene-2-oxatricyclo[4.3.0.01,3]nonan-8-yl]oxy-tri(propan-2-yl)silane
  参考文献：
  名称：

  A Tandem Cross-Metathesis/Semipinacol Rearrangement Reaction

  摘要：

  An efficient and (E)-selective synthesis of a 6-alkylidenebicyclo[3.2.1]octan-8-one has been developed. The key step is a tandem cross-metathesis/semipinacol rearrangement reaction, wherein the Hoveyda-Grubbs II catalyst, or more likely a derivative thereof, serves as the Lewis acid for the rearrangement. Despite the fact that both the starting alkene and the cross-metathesis product are viable rearrangement substrates, only the latter rearranges, suggesting that the Lewis acidic species is generated only after the cross-metathesis reaction is complete.

  DOI：

  10.1021/ol300691u

文献信息

• Design, Development, Mechanistic Elucidation, and Rational Optimization of a Tandem Ireland Claisen/Cope Rearrangement Reaction for Rapid Access to the (Iso)Cyclocitrinol Core
  作者：Christopher W. Plummer、Carolyn S. Wei、Carrie E. Yozwiak、Arash Soheili、Sara O. Smithback、James L. Leighton

  DOI：10.1021/ja505131v

  日期：2014.7.16

  (iso)cyclocitrinol core structure is described. The key step is a tandem Ireland Claisen/Cope rearrangement sequence, wherein the Ireland Claisen rearrangement effects ring contraction to a strained 10-membered ring, and that strain in turn drives the Cope rearrangement under unusually mild thermal conditions. A major side product was identified as resulting from an unexpected and remarkably facile [1,3]-sigmatropic

  描述了合成（异）环柠檬醇核心结构的方法。关键步骤是串联爱尔兰克莱森/科普重排序列，其中爱尔兰克莱森重排将环收缩影响为应变的 10 元环，而该应变又在异常温和的热条件下驱动 Cope 重排。一种主要的副产物被确定为出乎意料且非常容易的 [1,3]-σ 重排，并且合理地设计了一种不利于 [1,3] 途径并提高串联反应效率的策略。