MPAA | 1241962-14-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: MPAA
• CAS: 1241962-14-0
• 化学式: C₁₁H₁₁F₃O₃
• 分子量: 248.202
• InChiKey: VLCXHEVKQGLSOK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.34
• 重原子数：
  17.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  MPAA 在 o-nitrobenzenesulfonyl azide 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙腈 为溶剂， 反应 1.0h， 生成 2,2,2-trifluoroethyl 2-diazo-2-(4-methoxyphenyl)acetate
  参考文献：
  名称：

  CH官能化方法，用于合成手性C2对称的1,5-环辛二烯配体。

  摘要：

  手性环辛二烯（COD）衍生物很容易通过铑催化COD的烯丙基CH官能化来制备。COD的单官能化或双官能化都有可能以高收率，非对映选择性和对映选择性生成产物。双重CH官能化可生成具有两个新的立体异构中心的C2对称COD衍生物，这些中心的ee大于99％ee，可以容易地转化为一系列手性COD配体。初步评估表明，COD配体可用于铑催化的环己-2-烯酮的不对称芳基化反应，从而使共轭加成产物的ee高达76％。

  DOI：

  10.1021/acs.orglett.9b03764
• 作为产物：
  描述：

  2,2,2-三氟乙醇 、 4-methoxyphenacyl diphenyl phosphate 生成 MPAA
  参考文献：
  名称：

  Photophysics and Photodeprotection Reactions of p-Methoxyphenacyl Phototriggers: An Ultrafast and Nanosecond Time-Resolved Spectroscopic and Density Functional Theory Study

  摘要：

  Time-resolved spectroscopic experiments were performed to investigate the kinetics and mechanisms of the photodeprotection reactions for p-methoxyphenacyl (pMP) compounds, p-methoxyphenacyl diethyl phosphate (MPEP) and diphenyl phosphate (MPPP). The experimental results reveal that compared to the previous reports for the counterpart p-hydroxyphenacyl (pHP) phosphates, the (3)n pi*/pi pi* mixed character triplet of pMP acts as a reactive precursor that leads to the subsequent solvent and leaving group dependent chemical reactions and further affects the formation of photoproducts. The MPPP triplet in H2O/CH3CN and in fluorinated alcohols shows a rapid heterolytic cleavage (tau approximate to 5.4 ns) that results in deprotection and formation of a solvolytic rearrangement product, whereas the MPPP triplet in CH3CN and the MPEP triplet in CH3CN and H2O/CH3CN and fluorinated alcohols decay on a much longer time scale (tau approximate to 100 ns) with little observation of the rearrangement product. The density functional theory (DFT) calculations reveal a substantial solvation effect that is connected with the methoxy versus hydroxyl substitution in accounting for the different deprotection reactivity of pMP and pHP compounds. The results reported here provide new insight in elucidating the solvent and leaving group dependent dual reactivity of pMP compounds on the formation of the rearrangement versus reductive photoproduct.

  DOI：

  10.1021/jo100848b