8-benzyl-2-oxo-8-azabicyclo<3.2.1>oct-3-ene-6-exo-carbonitrile | 62215-46-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 8-benzyl-2-oxo-8-azabicyclo<3.2.1>oct-3-ene-6-exo-carbonitrile
• 英文别名: 8-benzyl-2-oxo-8-azabicyclo[3.2.1]oct-3-ene-6-carbonitrile；8-benzyl-2-oxo-8-azabicyclo[3.2.1]oct-3-ene-6-exo-carbonitrile；(1R,5R,6S)-8-benzyl-2-oxo-8-azabicyclo[3.2.1]oct-3-ene-6-carbonitrile
• CAS: 62215-46-7；62215-47-8；141583-52-0；141583-53-1
• 化学式: C₁₅H₁₄N₂O
• 分子量: 238.289
• InChiKey: GAVDNAIQJKWSSI-MGPQQGTHSA-N

物化性质

• 沸点：
  429.9±45.0 °C(Predicted)
• 密度：
  1.23±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  44.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  8-benzyl-2-oxo-8-azabicyclo<3.2.1>oct-3-ene-6-exo-carbonitrile 在 lithium aluminium tetrahydride 、 三乙胺 、 间氯过氧苯甲酸 作用下， 以 乙醚 、 氯仿 为溶剂， 反应 173.0h， 生成 8-benzyl-6-exo-(acetyloxy)-8-azabicyclo<3.2.1>octan-2-exo-ol
  参考文献：
  名称：

  Total synthesis of Bao Gong Teng A, a natural antiglaucoma compound

  摘要：

  The total synthesis of Bao Gong Tong A (1), a novel natural product which shows antiglaucoma properties is described. The key step involves the highly regioselective and somewhat stereoselective 1,3-dipolar cycloaddition of acrylonitrile to N-benzyl-3-hydroxypyridinium bromide 2 to give the easily separable crystalline exo and endo diastereomers 3x and 3n in yields of 54% and 36%, respectively. Catalytic hydrogenation of the enone of 3x followed by reduction with sodium borohydride gave, via the saturated ketone 4, the exo alcohol 5x in 54% overall yield along with a small amount of the endo stereoisomer 5n. Protection of the alcohol followed by addition of methyl Grignard produced, after hydrolysis of the intermediate imine and the silyl other, the desired 6-exo-acetyl-8-benzyl-8-azabicyclo [3.2.1]octan-2-exo-ol (8) in 71 % yield. The synthesis of Bao Gong Teng A (1) was completed by first effecting a Baeyer-Villiger oxidation of 8 to give N-benzyl Bao Gong Teng A (9) (54% yield) and then cleaving the N-benzyl group by hydrogenolysis to produce 1 in 74% yield, thereby ending an eight-step synthesis of Bao Gong Teng A (1) in 8% overall yield from readily available starting materials.

  DOI：

  10.1021/jo00039a005
• 作为产物：
  描述：

  3-羟基吡啶 、 alkaline earth salt of/the/ methylsulfuric acid 在 三乙胺 、 对苯二酚 作用下， 以 丙酮 为溶剂， 反应 20.0h， 生成 8-benzyl-2-oxo-8-azabicyclo<3.2.1>oct-3-ene-6-exo-carbonitrile
  参考文献：
  名称：

  Total synthesis of Bao Gong Teng A, a natural antiglaucoma compound

  摘要：

  The total synthesis of Bao Gong Tong A (1), a novel natural product which shows antiglaucoma properties is described. The key step involves the highly regioselective and somewhat stereoselective 1,3-dipolar cycloaddition of acrylonitrile to N-benzyl-3-hydroxypyridinium bromide 2 to give the easily separable crystalline exo and endo diastereomers 3x and 3n in yields of 54% and 36%, respectively. Catalytic hydrogenation of the enone of 3x followed by reduction with sodium borohydride gave, via the saturated ketone 4, the exo alcohol 5x in 54% overall yield along with a small amount of the endo stereoisomer 5n. Protection of the alcohol followed by addition of methyl Grignard produced, after hydrolysis of the intermediate imine and the silyl other, the desired 6-exo-acetyl-8-benzyl-8-azabicyclo [3.2.1]octan-2-exo-ol (8) in 71 % yield. The synthesis of Bao Gong Teng A (1) was completed by first effecting a Baeyer-Villiger oxidation of 8 to give N-benzyl Bao Gong Teng A (9) (54% yield) and then cleaving the N-benzyl group by hydrogenolysis to produce 1 in 74% yield, thereby ending an eight-step synthesis of Bao Gong Teng A (1) in 8% overall yield from readily available starting materials.

  DOI：

  10.1021/jo00039a005

文献信息

• Enantiodivergent Combination of Natural Product Scaffolds Enabled by Catalytic Enantioselective Cycloaddition
  作者：Hao Xu、Christopher Golz、Carsten Strohmann、Andrey P. Antonchick、Herbert Waldmann

  DOI：10.1002/anie.201602084

  日期：2016.6.27

  been established for the enantiodivergent synthesis of natural product inspired compounds embodying both tropane and pyrrolidine natural product fragments. This strategy includes the enantioselective kinetic resolution of racemic tropanes by means of a copper(I)‐catalyzed [3+2] cycloaddition and allows the preparation of two enantiopure products in a one‐pot reaction in high yield and with high diastereo‐

  已经建立了一种有效的策略，以对映体合成包含托烷和吡咯烷天然产物片段的天然产物激发的化合物。该策略包括通过铜（I）催化的[3 + 2]环加成反应得到外消旋对苯二酚的对映选择性动力学拆分，并允许在一个锅中以高收率，高非对映和对映选择性制备两种对映纯产物。通过使用一种手性催化剂。
• Estour, Francois; Rezel, Stephane; Fraisse, Didier, Heterocycles, 1999, vol. 50, # 2, p. 929 - 945
  作者：Estour, Francois、Rezel, Stephane、Fraisse, Didier、Metin, Jacques、Gaumet, Vincent、Lartigue, Claire、Miscoria, Gilles、Gueiffier, Alain、Blache, Yves、Teulade, Jean C.、Chavignon, Olivier

  DOI：——

  日期：——
• Preliminary Study of the Total Synthesis of Bao Gong Teng A Analogs Using 8-Benzyl-2-oxo-8-azabicyclo[3.2.1]oct-3-ene-6-endo/exo- and 7-endo/exo-carbonitrile
  作者：Olivier Chavignon、Stéphane Rézel、François Estour、Damien Canitrot、Elena V. Bejan Voinea、Jean-M. Chezal、Claire Lartigue、Yves Blache、Alain Gueiffier、Gérard Dauphin、Jean C. Teulade

  DOI：10.3987/com-98-8447

  日期：——
• DUCROT, P. -H.;LALLEMAND, J. Y., TETRAHEDRON LETT., 31,(1990) N7, C. 3879-3882
  作者：DUCROT, P. -H.、LALLEMAND, J. Y.

  DOI：——

  日期：——
• Total synthesis of Bao Gong Teng A, a natural antiglaucoma compound
  作者：Michael E. Jung、Longmei Zeng、Tangsheng Peng、Huiyan Zeng、Yan Le、Jingyu Su

  DOI：10.1021/jo00039a005

  日期：1992.6

  The total synthesis of Bao Gong Tong A (1), a novel natural product which shows antiglaucoma properties is described. The key step involves the highly regioselective and somewhat stereoselective 1,3-dipolar cycloaddition of acrylonitrile to N-benzyl-3-hydroxypyridinium bromide 2 to give the easily separable crystalline exo and endo diastereomers 3x and 3n in yields of 54% and 36%, respectively. Catalytic hydrogenation of the enone of 3x followed by reduction with sodium borohydride gave, via the saturated ketone 4, the exo alcohol 5x in 54% overall yield along with a small amount of the endo stereoisomer 5n. Protection of the alcohol followed by addition of methyl Grignard produced, after hydrolysis of the intermediate imine and the silyl other, the desired 6-exo-acetyl-8-benzyl-8-azabicyclo [3.2.1]octan-2-exo-ol (8) in 71 % yield. The synthesis of Bao Gong Teng A (1) was completed by first effecting a Baeyer-Villiger oxidation of 8 to give N-benzyl Bao Gong Teng A (9) (54% yield) and then cleaving the N-benzyl group by hydrogenolysis to produce 1 in 74% yield, thereby ending an eight-step synthesis of Bao Gong Teng A (1) in 8% overall yield from readily available starting materials.