(1R,4R,5S)-4-Phenyl-bicyclo[3.3.1]non-2-en-9-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1R,4R,5S)-4-Phenyl-bicyclo[3.3.1]non-2-en-9-one
• 英文别名: (1R,4R,5S)-4-phenylbicyclo[3.3.1]non-2-en-9-one
• 化学式: C₁₅H₁₆O
• 分子量: 212.291
• InChiKey: CUZXRTAQRCNXKD-RDBSUJKOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.4
• 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：

  1-吡咯烷-1-环己烯 、 alkaline earth salt of/the/ methylsulfuric acid 在 三氟乙酸 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 14.0h， 以71%的产率得到4-phenylbicyclo[3.3.1]non-2-en-9-one
  参考文献：
  名称：

  β,β'- 和 α,β,β'-环状烯胺的环化反应：Fischer 的双环[3.n.1] 烯酮 (n = 2, 3) 和三环[3.3.0.02,8]辛烷的对映选择性合成烯基卡宾配合物

  摘要：

  DOI：

  10.1021/ja002905i

文献信息

• Highly Diastereo- and Enantioselective Cu-Catalyzed [3 + 3] Cycloaddition of Propargyl Esters with Cyclic Enamines toward Chiral Bicyclo[<i>n</i>.3.1] Frameworks
  作者：Cheng Zhang、Xin-Hu Hu、Ya-Hui Wang、Zhuo Zheng、Jie Xu、Xiang-Ping Hu

  DOI：10.1021/ja303129s

  日期：2012.6.13

  Cu-catalyzed asymmetric [3 + 3] cycloaddition of propargyl esters with cyclic enamines is reported. With a combination of Cu(OAc)(2)·H(2)O and a chiral tridentate ferrocenyl-P,N,N ligand as the catalyst, perfect endo selectivities (endo/exo > 98/2) and excellent enantioselectivities (up to 98% ee) for endo cycloadducts were achieved under mild conditions. This method provides a simple and efficient approach

  报道了一种新的 Cu 催化的炔丙酯与环状烯胺的不对称 [3 + 3] 环加成反应。结合 Cu(OAc)(2)·H(2)O 和手性三齿二茂铁-P,N,N 配体作为催化剂，完美的内向选择性 (endo/exo > 98/2) 和出色的对映选择性 (up内环加合物达到 98% ee) 在温和条件下实现。该方法为合成光学活性双环[n.3.1]骨架提供了一种简单有效的方法。
• β,β‘- and α,β,β‘-Annulation Reactions of Cyclic Enamines:  Enantioselective Synthesis of Bicyclo[3.<i>n</i>.1]alkenones (<i>n</i> = 2, 3) and Tricyclo[3.3.0.0^2,8]octanes from Fischer Alkenyl Carbene Complexes
  作者：José Barluenga、Alfredo Ballesteros、Javier Santamaría、Ramón Bernardo de la Rúa、Eduardo Rubio、Miguel Tomás

  DOI：10.1021/ja002905i

  日期：2000.12.1
• Group 6 Heteroatom- and Non-Heteroatom-Stabilized Carbene Complexes. β,β‘- and α,β,β‘-Annulation Reactions of Cyclic Enamines
  作者：José Barluenga、Alfredo Ballesteros、Ramón Bernardo de la Rúa、Javier Santamaría、Eduardo Rubio、Miguel Tomás

  DOI：10.1021/ja0278077

  日期：2003.2.19

  Cyclization reactions of group 6 Fischer carbene complexes with cyclopentanone and cyclohexanone enamines are described. Enamine 3a undergoes thermal alpha,beta,beta'-annulation with alkenylcarbene complexes 1 and 2 (THF, 60degreesC), affording semibullvalenes 5. The metalate intermediates 6, resulting from beta,beta'-annulation of the enamines 3a and 4a, were quantitatively formed by running the reaction in hexane at room temperature. Acid-promoted demetalation of 6 afforded endo-2-bicyclo[3.2.1]octen-8-ones 7 and endolexo-2-bicyclo[3.3.1]nonen-9-ones 8 (endolexo = 5:1). Using (S)-methoxymethylpyrrolidine-derived enamines 3b and 4b,c allowed highly enantioenriched cycloadducts endo-(+)-7 as well as endo(-)-8 and exo-(-)-8 to be accessed. The non-heteroatom-stabilized carbene complex 10 was formed from complex 6 by Me3SiOTf-promoted elimination of the methoxy group, characterized by C-13 NMR, and transformed into the organic compounds 7, 7-d, and 11 as well as into bicyclo[3.2.1]octan-2,8-diones 14 and cycloheptanones 15. On the basis of this sequence, enantioenriched cycloheptanones (+)-15 were efficiently prepared in one pot from carbene complexes 2 and enamine 3b (51-55% yield, 91-96% ee). Extension of this work to simple Fischer carbene complexes 16 allowed an appropriate way to generate the nonstabilized pentacarbonyl[(phenyl(alkyl)carbene]tungsten complex 17 to be designed, for which the thermal and chemical behavior leading to compounds 18-21 is described.