4-methyloctahydrocyclopenta[1,4]cyclobuta[1,2]benzen-5(6H)-one | 82078-85-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-methyloctahydrocyclopenta[1,4]cyclobuta[1,2]benzen-5(6H)-one
• 英文别名: rac-(3aS,4R,4aS,8aR)-4-methyloctahydrocyclopenta[1,4]cyclobuta[1,2]benzen-5(6H)-one；(1S,5R,6S,7R)-6-methyltricyclo[5.4.0.01,5]undecan-8-one
• CAS: 82078-85-1
• 化学式: C₁₂H₁₈O
• 分子量: 178.274
• InChiKey: CILAGEUDZUHYTL-QCMRWSPLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-methyloctahydrocyclopenta[1,4]cyclobuta[1,2]benzen-5(6H)-one 在 间氯过氧苯甲酸 作用下， 以 氯仿 为溶剂， 以70%的产率得到(3aR,4S,4aR,9aS)-4-Methyl-octahydro-5-oxa-cyclopenta[1,4]cyclobuta[1,2]cyclohepten-6-one
  参考文献：
  名称：

  Intramolecular photoaddition of terminal allenes to conjugated cyclohexenones

  摘要：

  DOI：

  10.1021/jo00138a019
• 作为产物：
  描述：

  (Z)-6-bromohex-2-ene 在 magnesium 作用下， 以 环己烷 为溶剂， 反应 3.25h， 生成 4-methyloctahydrocyclopenta[1,4]cyclobuta[1,2]benzen-5(6H)-one
  参考文献：
  名称：

  Regiochemistry and stereochemistry of intramolecular [2+2] photocycloaddition of carbon-carbon double bonds to cyclohexenones

  摘要：

  The intramolecular [2 + 2] photocycloaddition mechanism of alkenes tethered by a three-methylene chain to cyclohexenones has been studied. It was found that the reversion from a 1,4-diradical intermediate to starting material is slow relative to the rate of photoadduct formation. Only ''straight'' closure was observed in the systems studied. For compounds 1-3 and 5, the assumption that the first bond is formed between the beta-carbon of the enone and C-4' leading to a 1,4-diradical is supported. For the formation of compounds 6-11, possible mechanisms are discussed.

  DOI：

  10.1021/jo00014a040

文献信息

• Intramolecular [2+2] Photocycloaddition of Cyclic Enones: Selectivity Control by Lewis Acids and Mechanistic Implications
  作者：Saner Poplata、Andreas Bauer、Golo Storch、Thorsten Bach

  DOI：10.1002/chem.201901304

  日期：2019.6.18

  that attractive dispersion forces may be responsible for a change of the binding mode. The catalytic [2+2] photocycloaddition was shown to proceed on the triplet hypersurface with a quantum yield of 0.05. The positive effect of Lewis acids on the outcome of a given intramolecular [2+2] photocycloaddition was illustrated by optimizing the key step in a concise total synthesis of the sesquiterpene (±)‐italicene

  在存在λ = 366 nm的条件下进行辐照时，以对映选择性的方式进行3-烯基-2-环烯酮的分子内[2 + 2]光环加成反应（九个代表性实例，产率为54-86％，ee为76-96％ee）。 AlBr 3活化的恶唑硼烷作为路易斯酸。对脯氨酸衍生的恶唑硼烷的广泛筛选表明，对映体的分化很大程度上取决于杂环3位上芳基的性质。路易斯酸-底物复合物的DFT计算表明，有吸引力的分散力可能是改变结合模式的原因。催化的[2 + 2]光环加成反应在三重态超表面上进行，量子产率为0.05。通过优化倍半萜烯（±）-斜体的简明全合成中的关键步骤，可以说明路易斯酸对给定的分子内[2 + 2]光环加成反应的积极作用。
• Brønsted Acid Catalysis in Visible-Light-Induced [2+2] Photocycloaddition Reactions of Enone Dithianes
  作者：Christoph Brenninger、Alexander Pöthig、Thorsten Bach

  DOI：10.1002/anie.201700837

  日期：2017.4.3

  1,3-Dithiane-protected enones (enone dithianes) were found to undergo an intramolecular [2+2] photocycloaddition under visible-light irradiation (λ=405 nm) in the presence of a Brønsted acid (7.5-10 mol %). Key to the success of the reaction is presumably the formation of colored thionium ions, which are intermediates of the catalytic cycle. Cyclobutanes were thus obtained in very good yields (78-90 %)

  发现 1,3-二噻烷保护的烯酮（烯酮二噻烷）在可见光照射（λ=405 nm）下、在布朗斯台德酸（7.5-10 mol%）存在下发生分子内 [2+2] 光环加成。该反应成功的关键可能是有色锍离子的形成，它们是催化循环的中间体。由此以非常好的收率（78-90%）获得环丁烷。还表明，二噻烷部分可以被还原或氧化去除，而不影响光化学构建的环骨架。
• Intramolecular [2 + 2] photocycloadditions of E and Z olefins to cyclohex-2-enone
  作者：Dan Becker、Meshulam Nagler、Sara Hirsh、Jean Ramun

  DOI：10.1039/c39830000371

  日期：——

  The [2 + 2] intramolecular photocycloaddition of E and Z olefins to a cyclohexenone has been investigated; it is concluded that the bond to C(3) in the cyclohexenone is formed first to give the diradical intermediates (7a) and (7b).

  研究了E和Z烯烃与环己烯酮的[2 + 2]分子内光环加成；结论是，首先形成与环己烯酮中的C（3）的键，得到双自由基中间体（7a）和（7b）。
• Regiochemistry and stereochemistry of intramolecular [2+2] photocycloaddition of carbon-carbon double bonds to cyclohexenones
  作者：D. Becker、M. Nagler、Y. Sahali、N. Haddad

  DOI：10.1021/jo00014a040

  日期：1991.7

  The intramolecular [2 + 2] photocycloaddition mechanism of alkenes tethered by a three-methylene chain to cyclohexenones has been studied. It was found that the reversion from a 1,4-diradical intermediate to starting material is slow relative to the rate of photoadduct formation. Only ''straight'' closure was observed in the systems studied. For compounds 1-3 and 5, the assumption that the first bond is formed between the beta-carbon of the enone and C-4' leading to a 1,4-diradical is supported. For the formation of compounds 6-11, possible mechanisms are discussed.
• Intramolecular photoaddition of terminal allenes to conjugated cyclohexenones
  作者：Dan Becker、Zvi Harel、Meshulam Nagler、Arie Gillon

  DOI：10.1021/jo00138a019

  日期：1982.8