endo-cis-(isopropylidenedioxy)-7-oxabicyclo[2.2.1]hept-5-ene | 135505-68-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: endo-cis-(isopropylidenedioxy)-7-oxabicyclo[2.2.1]hept-5-ene
• 英文别名: (1R,2S,6R,7S)-4,4-dimethyl-3,5,10-trioxatricyclo[5.2.1.02,6]dec-8-ene
• CAS: 135505-68-9
• 化学式: C₉H₁₂O₃
• 分子量: 168.192
• InChiKey: JFBVYKQZGOOEIC-SOSBWXJGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.84
• 重原子数：
  12.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  27.69
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  endo-cis-(isopropylidenedioxy)-7-oxabicyclo[2.2.1]hept-5-ene 在 bis(1,5-cyclooctadiene)nickel (0) 、 二异丁基氢化铝 、 (R)-2,2'-bis(diphenylphosphanyl)-1,1'-binaphthyl 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 6.0h， 生成 (3aR,4S,7aS)-2,2-dimethyl-3a,4,5,7a-tetrahydrobenzo[d][1,3]-dioxol-4-ol 、 (1R,2S,3R)-2,3-O-isopropylidenecyclohex-4-ene-1,2,3-triol
  参考文献：
  名称：

  镍催化的不对称还原性开环反应的范围。对映体富集的环己醇的合成

  摘要：

  在催化量的Ni（COD）2和（R）-BINAP存在下，使各种氧杂双环[2.2.1]庚烯经历二异丁基氢化铝（DIBAL-H）导致高度对映选择性的开环，与ee's生成环己烯醇通常大于90％。已经确定了该反应的范围，并且已经研究了比Ni（COD）2敏感度低的替代镍催化剂。

  DOI：

  10.1016/s0040-4020(97)10211-3
• 作为产物：
  描述：

  7-Oxabicyclo<2.2.1>hept-5-en-endo-2,endo-3-diol 、 2,2-二甲氧基丙烷 在 对甲苯磺酸 作用下， 以 丙酮 为溶剂， 反应 3.0h， 以81%的产率得到endo-cis-(isopropylidenedioxy)-7-oxabicyclo[2.2.1]hept-5-ene
  参考文献：
  名称：

  Living ring-opening metathesis polymerization of 2,3-difunctionalized 7-oxanorbornenes and 7-oxanorbornadienes by Mo(CHCMe2R)(NC6H3-iso-Pr2-2,6)(O-tert-Bu)2 and Mo(CHCMe2R)(NC6H3-iso-Pr2-2,6)(OCMe2CF3)2

  摘要：

  7-Oxabenzonorbornadiene (9), 2,3-endo-cis-diacetoxy-7-oxanorbornene, and 2,3-endo-cis-(isopropylidenedioxy)-7-oxanorbornene can be polymerized by Mo(CHCMe2R)(NAr)(O-t-Bu)2 (Ar = 2,6-C6H3-i-Pr2; R = CH3, C6H5) ([Mo]-(CHCMe2R)) to give polymers with narrow molecular weight distributions (PDI < 1.17). However, 2,3-bis(trifluoromethyl)-7-oxanorbornadiene (1), 2,3-dicarbomethoxy-7-oxanorbornadiene (4), and 2,3-trans-dicyano-7-oxanorborn-5-ene (12) form stable metallacycles upon addition to [Mo](CHCMe2R). The rate of reaction of 1 with [Mo](CHCMe2R) has been determined qualitatively to be comparable to that of norbornene in competition experiments, a result that implies that the lone pair on the oxygen in the 7-position is accelerating metallacycle formation. The metallacycle that results from addition of 1 to [Mo](CHCMe2Ph) is square pyramidal with the imido ligand in the apical position. (Crystal data for 2b: a = 12.420 (3) angstrom, b = 15.466 (4) angstrom, c = 20.856 (6) angstrom, V = 3852 (2) angstrom 3, beta = 105.97 (2)degrees, space group = P2(1)/n, Z = 4, M(r) = 779.76, rho = 1.345 g/cm3, mu = 3.9 cm-1, R1 = 0.049, R2 = 0.068.) The MoC3 ring is planar with the CMe2Ph group pointed toward the imido ligand and the C-7 frame of the monomer pointed away from it (a trans metallacyclic ring). The oxygen in the 7-position of the norbornene moiety is located 3.332 (4) angstrom from the metal. Electronic and steric factors that influence first-order breakup of the metallacycle have been studied for monomers 1 and 4. The more reactive catalyst, Mo(CHCMe2Ph)(NAr)(OCMe2CF3)2, can polymerize 1, 4, and 12 to give polymers with narrow molecular weight distributions (PDI < 1.15).

  DOI：

  10.1021/ja00018a028