1,2,3,4,4a,9a-hexahydro-1,4-methanofluoren-9-one | 34139-44-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 1,2,3,4,4a,9a-hexahydro-1,4-methanofluoren-9-one
• 英文别名: (1R,2S,10R,11S)-tetracyclo[9.2.1.02,10.03,8]tetradeca-3,5,7-trien-9-one
• CAS: 34139-44-1
• 化学式: C₁₄H₁₄O
• 分子量: 198.265
• InChiKey: AAYGMVIISWIUBV-OTMMVIPVSA-N

物化性质

• 熔点：
  51-53 °C
• 沸点：
  308.6±12.0 °C(Predicted)
• 密度：
  1.196±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  降冰片烯 在 palladium diacetate 、 二甲基硫 、 thallium(I) acetate 、 臭氧 、 三苯基膦 作用下， 以 乙腈 为溶剂， 反应 63.25h， 生成 1,2,3,4,4a,9a-hexahydro-1,4-methanofluoren-9-one
  参考文献：
  名称：

  Palladium catalysed cyclisation- intermolecular cyclopropanation versus cyclisation Friedel- Crafts alkylation with olefin insertion

  摘要：

  Palladium catalysed cascade processes involving formation of two new rings and three new bonds with incorporation of norbornene are described. Factors influencing 3 - versus 5-membered rings are identified. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(98)00022-2

文献信息

• Carbopalladation of Nitriles:  Synthesis of 2,3-Diarylindenones and Polycyclic Aromatic Ketones by the Pd-Catalyzed Annulation of Alkynes and Bicyclic Alkenes by 2-Iodoarenenitriles
  作者：Alexandre A. Pletnev、Qingping Tian、Richard C. Larock

  DOI：10.1021/jo026178g

  日期：2002.12.1

  represents one of the first examples of the addition of an organopalladium moiety to the carbon-nitrogen triple bond of a nitrile. The reaction is compatible with a number of functional groups. A reaction mechanism, as well as a model accounting for the electronic effects of substituents on the aromatic ring of the nitrile, is proposed.

  2-碘苄腈，其衍生物和各种杂环类似物在二芳基乙炔或双环烯烃上进行钯（0）催化的环化反应，从而以非常好的至极好的收率得到2,3-二芳基萘和多环芳族酮。该反应代表将有机钯部分加成到腈的碳-氮三键上的第一个例子。该反应与许多官能团相容。提出了反应机理以及考虑取代基对腈芳环电子效应的模型。
• Palladium‐Catalyzed Annulation of Acyl Fluorides with Norbornene via Decarbonylation and CO Reinsertion
  作者：Yuka Sakurai、Yohei Ogiwara、Norio Sakai

  DOI：10.1002/chem.202001374

  日期：2020.10.9

  A palladium‐catalyzed annulation of acyl fluorides with norbornene is described. This study reports the first example of an annulation of acyl fluorides in the presence of a transition‐metal catalyst. Polycyclic ketones are obtained from the cleavage of the C−F and C−H bonds of the acyl fluoride and the rearrangement of the carbonyl moiety by decarbonylation and CO reinsertion.

  描述了钯催化的降冰片烯酰氟氟化。这项研究报告了在过渡金属催化剂存在下酰氟环化的第一个例子。多环酮是通过酰基氟的CF键和CH键的裂解以及羰基部分的脱羰和CO的重新插入而获得的。
• Nickel-Catalyzed Reaction of Benzamides with Bicylic Alkenes: Cleavage of C–H and C–N Bonds
  作者：Aymen Skhiri、Naoto Chatani

  DOI：10.1021/acs.orglett.9b00351

  日期：2019.3.15

  The nickel-catalyzed reaction of aromatic amides that contain an 8-aminoquinoline as a directing group with bicyclic alkenes, such as norbornene and 1,4-dihydro-1,4-epoxynaphthalene, results in the cleavage of both the C–H bond at the ortho-position of the benzene ring and the C(O)–N bond to give methanofluoren-9-one and 1,4-epoxyfluoren-9-one derivatives. Both Ni(OTf)2 and Ni(cod)2 show a high catalytic

  含8-氨基喹啉作为导向基团的芳族酰胺与双环烯烃（如降冰片烯和1,4-二氢-1,4-环氧萘）的镍催化反应导致两个CH键在C原子上断裂苯环和C（O）–N键的邻位可得到甲氧芴9-one和1,4-环氧芴9-one衍生物。Ni（OTf）2和Ni（cod）2均显示出高催化活性。AgOAc的存在对于反应进行至关重要。在间位取代的芳族酰胺中，受阻较小的C–H键专门被官能化。
• Rhodium-Catalyzed Coupling Reaction of Aroyl Chlorides with Alkenes
  作者：Toru Sugihara、Tetsuya Satoh、Masahiro Miura、Masakatsu Nomura

  DOI：10.1002/adsc.200404145

  日期：2004.12

  Aroyl chlorides react with acyclic and cyclic alkenes in the presence of a rhodium catalyst to give Mizoroki–Heck type and cyclization products, respectively. A rhodium-ethylene complex, [RhCl(C2H4)2}2], showed excellent performance for these reactions. Notably, the reactions can be conducted effectively under base- and phosphane-free conditions.

  在铑催化剂的存在下，芳酰氯与无环和环状烯烃反应，分别得到Mizoroki-Heck型和环化产物。铑-乙烯络合物[RhCl（C 2 H 4）2 } 2 ]显示出对于这些反应的优异性能。值得注意的是，该反应可以在无碱和无膦的条件下有效地进行。
• Rhodium(I)-Catalyzed Carbonylative Annulation of Iodobenzenes with Strained Olefins and 4-Octyne in the Presence of Furfural Involving<i>ortho</i>-C-H Bond Cleavage
  作者：Takuma Furusawa、Hiroki Tanimoto、Yasuhiro Nishiyama、Tsumoru Morimoto、Kiyomi Kakiuchi

  DOI：10.1002/adsc.201601056

  日期：2017.1.19

  rhodium(I)‐catalyzed carbonylative annulation of iodobenzenes with strained olefins in the presence of furfural as a carbonyl source, accompanied by ortho‐C–H bond cleavage, is reported. The use of 4‐octyne in place of strained olefins also leads to the formation of the corresponding inden‐9‐one. The timely release of the carbonyl moiety via the rhodium‐catalyzed decarbonylation of furfural plays a decisive

  据报道，在糠醛作为羰基来源存在的情况下，铑（I）催化的碘代苯与应变烯烃的羰基化环化反应，伴随着邻-C-H键断裂。使用4-辛炔代替应变烯烃也会导致相应的茚满9-1的形成。通过铑催化的糠醛脱羰基及时释放羰基在该反应中起决定性作用。