8-benzyl-2-exo-<(trimethylsilyl)oxy>-8-azabicyclo<3.2.1>octane-6-exo-carbonitrile | 141557-07-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: 8-benzyl-2-exo-<(trimethylsilyl)oxy>-8-azabicyclo<3.2.1>octane-6-exo-carbonitrile
• 英文别名: 8-benzyl-2-exo--8-azabicyclo<3.2.1>octane-6-exo-carbonitrile；8-benzyl-2-exo-[(trimethylsilyl)oxy]-8-azabicyclo[3.2.1]octane-6-exo-carbonitrile；(1R,2S,5R,6S)-8-benzyl-2-trimethylsilyloxy-8-azabicyclo[3.2.1]octane-6-carbonitrile
• CAS: 141557-07-5
• 化学式: C₁₈H₂₆N₂OSi
• 分子量: 314.503
• InChiKey: IVDGPZCCFUTUBP-TVFCKZIOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.78
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  36.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  8-benzyl-2-exo-<(trimethylsilyl)oxy>-8-azabicyclo<3.2.1>octane-6-exo-carbonitrile 在 间氯过氧苯甲酸 作用下， 以 氯仿 为溶剂， 反应 168.0h， 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：

  1-benzyl-3-hydroxypyridinium bromide 在 钯 sodium tetrahydroborate 、 氢气 、 三乙胺 、 对苯二酚 作用下， 以 甲醇 、 乙醚 为溶剂， 25.0 ℃ 、101.33 kPa 条件下， 反应 47.0h， 生成 8-benzyl-2-exo-<(trimethylsilyl)oxy>-8-azabicyclo<3.2.1>octane-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

• 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：——
• 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.