| 1357175-33-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• CAS: 1357175-33-7
• 化学式: C₁₅H₁₄O₄*C₄₈H₈₀O₄₀
• 分子量: 1555.41
• InChiKey: GETKTZYHVPNFHX-REIXHVNVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -14.85
• 重原子数：
  107.0
• 可旋转键数：
  11.0
• 环数：
  32.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  685.8
• 氢给体数：
  24.0
• 氢受体数：
  44.0

反应信息

• 作为反应物：
  描述：

  反应 6.0h， 生成 、 、 、 、 、
  参考文献：
  名称：

  Enhancement of Diastereoselectivity in Photodimerization of Alkyl 2-Naphthoates with Chiral Auxiliaries via Inclusion within γ-Cyclodextrin Cavities

  摘要：

  Irradiations of alkyl 2-naphthoates are known to result in four isomeric "cubane-like" photodimers: anti(HH)-2, syn(HH)-2, anti(HT)-2, and syn(HT)-2 where the anti(HH)-2, anti(HT)-2, and syn(HT)-2 consist of pairs of diastereomers. Here, chiral auxiliary and chiral microreactor strategies have been combined to achieve high diastereoselectivity in photo-dimerizations of an enantiomeric pair of 2-naphthoates with (R)- and (S)-1-methoxycarbonylethyl esters as chiral auxiliaries (1R and 1S). Thus, irradiations of their gamma-cyclodextrin (gamma-CD) complexes have been conducted. Fluorescence, IR, and NMR spectra of both enantiomers of I demonstrate that their gamma-CD complexes are mainly 2:2 with the molecules of 1 in head-to-head orientations. Irradiation of the complexes in the solid state mainly resulted in anti(HH)-2. The absolute configuration of each diastereomer of anti(HH)-2 has been established for the first time here. The diastereomeric excesses (de's) of anti(HH)-2 from IR and 15 were 94% and 86%, respectively. These de's are much higher than those found from irradiations in solution (55% for IR and 1S), where the opposite diastereomeric form is in excess! Calculations of the energies of various conformations of the head-to-head 2:2 inclusion complexes were performed using the PM3 approach. The predicted major diastereomers based on the calculation are consistent with those found experimentally.

  DOI：

  10.1021/jo2020328
• 作为产物：
  描述：

  [(2R)-1-methoxy-1-oxopropan-2-yl] naphthalene-2-carboxylate 、 γ-环糊精 以 二氯甲烷 、 水 为溶剂， 生成
  参考文献：
  名称：

  Enhancement of Diastereoselectivity in Photodimerization of Alkyl 2-Naphthoates with Chiral Auxiliaries via Inclusion within γ-Cyclodextrin Cavities

  摘要：

  Irradiations of alkyl 2-naphthoates are known to result in four isomeric "cubane-like" photodimers: anti(HH)-2, syn(HH)-2, anti(HT)-2, and syn(HT)-2 where the anti(HH)-2, anti(HT)-2, and syn(HT)-2 consist of pairs of diastereomers. Here, chiral auxiliary and chiral microreactor strategies have been combined to achieve high diastereoselectivity in photo-dimerizations of an enantiomeric pair of 2-naphthoates with (R)- and (S)-1-methoxycarbonylethyl esters as chiral auxiliaries (1R and 1S). Thus, irradiations of their gamma-cyclodextrin (gamma-CD) complexes have been conducted. Fluorescence, IR, and NMR spectra of both enantiomers of I demonstrate that their gamma-CD complexes are mainly 2:2 with the molecules of 1 in head-to-head orientations. Irradiation of the complexes in the solid state mainly resulted in anti(HH)-2. The absolute configuration of each diastereomer of anti(HH)-2 has been established for the first time here. The diastereomeric excesses (de's) of anti(HH)-2 from IR and 15 were 94% and 86%, respectively. These de's are much higher than those found from irradiations in solution (55% for IR and 1S), where the opposite diastereomeric form is in excess! Calculations of the energies of various conformations of the head-to-head 2:2 inclusion complexes were performed using the PM3 approach. The predicted major diastereomers based on the calculation are consistent with those found experimentally.

  DOI：

  10.1021/jo2020328