6-methoxy-1,2,3,4,4a,9a-hexahydro-1,4-methanofluoren-9-one | 490039-92-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 6-methoxy-1,2,3,4,4a,9a-hexahydro-1,4-methanofluoren-9-one
• 英文别名: rac-(1R,4S,4aR,9aS)-6-methoxy-1,2,3,4,4a,9a-hexahydro-9H-1,4-methanofluoren-9-one；1,2,3,4,4a,9a-hexahydro-6-methoxy-1,4-methanofluoren-9-one；(1R,2S,10R,11S)-5-methoxytetracyclo[9.2.1.02,10.03,8]tetradeca-3(8),4,6-trien-9-one
• CAS: 490039-92-4
• 化学式: C₁₅H₁₆O₂
• 分子量: 228.291
• InChiKey: AKBRGPALYPJQNO-HZZFPTLFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  降冰片烯 、 1-(2-iodo-4-methoxyphenyl)pentan-1-one 在 dibromo[1,2-bis(diphenylphosphino)ethane]nickel(II) 锌 作用下， 以 乙腈 为溶剂， 反应 12.0h， 以63%的产率得到6-methoxy-1,2,3,4,4a,9a-hexahydro-1,4-methanofluoren-9-one
  参考文献：
  名称：

  Facile β-Alkyl and β-Hydride Elimination in the Nickel-Catalyzed Annulation of o-Iodophenyl Ketones and Aldehydes with Bicyclic Alkenes

  摘要：

  o-Iodoaryl aldehydes react with bicyclic alkenes in the presence of NiBr2(dppe) and Zn powder in acetonitrile at 80 degrees C undergoing annulation to give polycyclic ketone derivatives. Surprisingly, o-iodoaryl alkyl ketones also react with bicyclic alkenes to form polycyclic ketones with structures the same as those from the corresponding o-iodoaryl aldehydes.

  DOI：

  10.1021/ol061051p

文献信息

• 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(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。