(1S,2R,5R)-2-[(S)-(tert-Butyl-dimethyl-silanyloxy)-phenyl-methyl]-8-methyl-8-aza-bicyclo[3.2.1]octan-3-one | 167415-14-7

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 托烷生物碱
• 英文名称: (1S,2R,5R)-2-[(S)-(tert-Butyl-dimethyl-silanyloxy)-phenyl-methyl]-8-methyl-8-aza-bicyclo[3.2.1]octan-3-one
• 英文别名: (1S,2R,5R)-2-[(S)-[tert-butyl(dimethyl)silyl]oxy-phenylmethyl]-8-methyl-8-azabicyclo[3.2.1]octan-3-one
• CAS: 167415-14-7
• 化学式: C₂₁H₃₃NO₂Si
• 分子量: 359.584
• InChiKey: PNGYVOHXKOMNFQ-LCLWPZTBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  25
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1S,2R,5R)-2-[(S)-(tert-Butyl-dimethyl-silanyloxy)-phenyl-methyl]-8-methyl-8-aza-bicyclo[3.2.1]octan-3-one 在 platinum(IV) oxide 氢气 、 silica gel 作用下， 以 乙醇 、 正己烷 、 乙酸乙酯 为溶剂， 反应 66.0h， 生成 (1S,2R,3S,5R)-2-[(R)-(tert-Butyl-dimethyl-silanyloxy)-phenyl-methyl]-8-methyl-8-aza-bicyclo[3.2.1]octan-3-ol
  参考文献：
  名称：

  Synthesis of Tropane Alkaloids via Enantioselective Deprotonation of Tropinone

  摘要：

  Enantioselective deprotonation of tropinone 2 with chiral lithium amides 5a and 6a, in the presence of LiCl, gave tropinone lithium enolate in up to 95% ee. The C-2 symmetrical lithium amide 6a worked best when it was generated in situ from the hydrochloride salt of the corresponding amine 6b. The deprotonation was used as the key step in synthesis of tropane alkaloids: ent-anhydroecgonine, ent-knightinol, KD-B, chalcostrobamine, ent-isobellendine, and ent-darlingine. The absolute configuration of natural benzyltropane and pyranotropane alkaloids was established (by correlation with anhydroecgonine) to be 'cocaine-like' i.e., the side chain originates at C-2 of the tropane ring system in all cases.

  DOI：

  10.1021/jo00123a018
• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 、 (1S)-2-(1'-Hydroxybenzyl)-8-methyl-8-azabicyclo<3.2.1>octan-3-one 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 16.0h， 以87%的产率得到(1S,2R,5R)-2-[(S)-(tert-Butyl-dimethyl-silanyloxy)-phenyl-methyl]-8-methyl-8-aza-bicyclo[3.2.1]octan-3-one
  参考文献：
  名称：

  Synthesis of Tropane Alkaloids via Enantioselective Deprotonation of Tropinone

  摘要：

  Enantioselective deprotonation of tropinone 2 with chiral lithium amides 5a and 6a, in the presence of LiCl, gave tropinone lithium enolate in up to 95% ee. The C-2 symmetrical lithium amide 6a worked best when it was generated in situ from the hydrochloride salt of the corresponding amine 6b. The deprotonation was used as the key step in synthesis of tropane alkaloids: ent-anhydroecgonine, ent-knightinol, KD-B, chalcostrobamine, ent-isobellendine, and ent-darlingine. The absolute configuration of natural benzyltropane and pyranotropane alkaloids was established (by correlation with anhydroecgonine) to be 'cocaine-like' i.e., the side chain originates at C-2 of the tropane ring system in all cases.

  DOI：

  10.1021/jo00123a018

文献信息

• Determination of the relative configuration of tropinone and granatanone aldols by using TBDMS ethers
  作者：Ryszard Lazny、Aneta Nodzewska、Katarzyna Sidorowicz、Przemyslaw Kalicki

  DOI：10.3762/bjoc.8.216

  日期：——

  diastereomers (exo,anti to endo,syn and exo,syn to endo,anti). The exo forms invert to endo isomers in the presence of silica gel. The relative configuration of a new isomer of tropinone aldol accessible synthetically through the direct solventless reaction of tropinone and benzaldehyde in the presence of water was determined as exo,syn by comparison of NMR data of the aldol isomers, in particular vicinal coupling

  托品酮醛醇（8-甲基-8-氮杂双环[3.2.1]辛烷-3-酮）的所有四种非对映异构体的叔丁基二甲基甲硅烷基（TBDMS）醚的相对构型，以及格拉纳酮（9-甲基- 9-氮杂双环[3.3.1]壬烷-3-one)，由核磁共振数据和观察到的非对映异构体的相互转化（外向，反内向，syn 和外向，syn 向内，反）确定。在硅胶存在下，外型转化为内型异构体。通过比较羟醛异构体的 NMR 数据，特别是相应的邻位偶联常数和位移，将通过托品酮和苯甲醛在水存在下的直接无溶剂反应合成得到的托品酮醛醇的新异构体的相对构型被确定为 exo,syn到侧链 CH 基团，