8-phenylselenomethyl-cis-7-oxabicyclo<4.3.0>nonane

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并呋喃
• 英文名称: 8-phenylselenomethyl-cis-7-oxabicyclo<4.3.0>nonane
• 英文别名: (3aS,7aS)-2-(phenylselanylmethyl)-2,3,3a,4,5,6,7,7a-octahydro-1-benzofuran
• 化学式: C₁₅H₂₀OSe
• 分子量: 295.283
• InChiKey: MARMJCZKNUKENR-YOYPFHDYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.78
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  甲醇 、 8-phenylselenomethyl-cis-7-oxabicyclo<4.3.0>nonane 在 萘-1,4-二腈 作用下， 反应 8.0h， 以78%的产率得到(3aS,7aS)-2-Methoxymethyl-octahydro-benzofuran
  参考文献：
  名称：

  Photoinduced Electron Transfer Initiated Activation of Organoselenium Substrates as Carbocation Equivalents: Sequential One-Pot Selenylation and Deselenylation Reaction

  摘要：

  The investigation presented in this paper explores the mechanistic aspects and synthetic potentials of PET activation of organoselenium substrates. Fluorescence quenching of (DCN)-D-1* by a number of organoselenium compounds (RCH(2)SeR', 1-4), correlation of the fluorescence quenching rate constants with the oxidation potentials of 1-4, and the dependence of photodissociation quantum yields of 1-4 on their concentration suggests the occurrence of electron transfer processes between (DCN)-D-1* and 1-4. Steady-state photolysis of 1-4 in the presence of (DCN)-D-1* leads to the efficient one-electron oxidative heterolytic dissociation of the carbon-selenium bond to produce the carbocation (RCH(2)(+) or equivalent) and radical-centered selenium species (R'Se-.) via the intermediacy of cation-radical [(RCH(2)SeR')(+.)]. Nucleophilic assistance in the fragmentation of (RCH(2)SeR')(+.) by methanol has been suggested on the basis of products obtained from the control PET reaction of neopentyl phenyl selenide (8). The synthetic utility of these findings has been demonstrated for the deselenylation (Table 4) as well as one-spot sequential selenylation-deselenylation (Table 5) reactions.

  DOI：

  10.1021/jo00103a031
• 作为产物：
  描述：

  cis-2-allylcyclohexanol 、 phenyl trifluoromethaneselenosulfonate 以 二氯甲烷 为溶剂， 以83%的产率得到8-phenylselenomethyl-cis-7-oxabicyclo<4.3.0>nonane
  参考文献：
  名称：

  Stereoselective formation of tetrahydrofuran and -pyran by benzeneselenenyl triflate

  摘要：

  DOI：

  10.1016/s0040-4039(00)96525-0

文献信息

• Photoinduced single electron transfer initiated heterolytic carbon-selenium bond dissociation. Sequential one-pot selenenylation and deselenenylation reaction
  作者：Ganesh Pandey、B. B. V. Soma Sekhar、U. T. Bhalerao

  DOI：10.1021/ja00170a045

  日期：1990.7
• Inoue, Hirofumi; Murata, Shizuaki, Heterocycles, 1997, vol. 45, # 5, p. 847 - 850
  作者：Inoue, Hirofumi、Murata, Shizuaki

  DOI：——

  日期：——
• In situ generation and utilization of electrophilic selenium species (PhSe+) by photooxidative (single electron transfer) cleavage of diphenyl diselenide (PhSeSePh)
  作者：Ganesh Pandey、B. B. V. Soma Sekhar

  DOI：10.1021/jo00040a054

  日期：1992.7
• Photoinduced Electron Transfer Initiated Activation of Organoselenium Substrates as Carbocation Equivalents: Sequential One-Pot Selenylation and Deselenylation Reaction
  作者：Ganesh Pandey、B. B. V. Soma Sekhar

  DOI：10.1021/jo00103a031

  日期：1994.12

  The investigation presented in this paper explores the mechanistic aspects and synthetic potentials of PET activation of organoselenium substrates. Fluorescence quenching of (DCN)-D-1* by a number of organoselenium compounds (RCH(2)SeR', 1-4), correlation of the fluorescence quenching rate constants with the oxidation potentials of 1-4, and the dependence of photodissociation quantum yields of 1-4 on their concentration suggests the occurrence of electron transfer processes between (DCN)-D-1* and 1-4. Steady-state photolysis of 1-4 in the presence of (DCN)-D-1* leads to the efficient one-electron oxidative heterolytic dissociation of the carbon-selenium bond to produce the carbocation (RCH(2)(+) or equivalent) and radical-centered selenium species (R'Se-.) via the intermediacy of cation-radical [(RCH(2)SeR')(+.)]. Nucleophilic assistance in the fragmentation of (RCH(2)SeR')(+.) by methanol has been suggested on the basis of products obtained from the control PET reaction of neopentyl phenyl selenide (8). The synthetic utility of these findings has been demonstrated for the deselenylation (Table 4) as well as one-spot sequential selenylation-deselenylation (Table 5) reactions.
• Stereoselective formation of tetrahydrofuran and -pyran by benzeneselenenyl triflate
  作者：Shizuaki Murata、Toshiyasu Suzuki

  DOI：10.1016/s0040-4039(00)96525-0

  日期：——