<1S-(1β,9β,9a-β)>-1-(Benzoyloxy)octahydro-9-hydroxy-4H-quinolizin-4-one | 155768-67-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹嗪类
• 英文名称: <1S-(1β,9β,9a-β)>-1-(Benzoyloxy)octahydro-9-hydroxy-4H-quinolizin-4-one
• 英文别名: (-)-(1S,9R,9aR)-1-benzoyloxy-9-hydroxy-1,2,3,6,7,8,9,9a-octahydro-4H-quinolizin-4-one；[(1S,9R,9aR)-9-hydroxy-4-oxo-1,2,3,6,7,8,9,9a-octahydroquinolizin-1-yl] benzoate
• CAS: 155768-67-5
• 化学式: C₁₆H₁₉NO₄
• 分子量: 289.331
• InChiKey: LXJKHNLXHWHUIB-VNHYZAJKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  66.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  <1S-(1β,9β,9a-β)>-1-(Benzoyloxy)octahydro-9-hydroxy-4H-quinolizin-4-one 在 dimethyl sulfide borane 作用下， 以 四氢呋喃 为溶剂， 以38%的产率得到<1S-(1β,9β,9a-β)>-Octahydro-2H-quinolizine-1,9-diol
  参考文献：
  名称：

  Synthesis of Chiral Hydroxylated Quinolizidines via Vinylogous Bischler-Napieralski Nitrilium Ion Cyclizations

  摘要：

  Treatment of the amido esters 9 and 17 with PPSE (polyphosphoric acid trimethylsilyl ester) followed by NaBH4 in ethanol gave the quinolizidinones 11-14 and 19 via a vinylogous Bischler-Napieralski nitrilium ion cyclization-reductive lactamization two-step process. Subsequent ozonolysis and reduction afforded chiral hydroxylated quinolizidines in moderate to good yield. In contrast to five-membered-ring formation, six-membered-ring formation via nitrilium-ion cyclization requires a p-methoxy-substituted styryl terminator. The effect para-substituted styryl terminators have on the energy of activation and Delta H for the cyclization process has been calculated by semiempirical and ab initio methods.

  DOI：

  10.1021/jo00087a026
• 作为产物：
  描述：

  (S)-(+)-5-氧代-2-四氢呋喃羧酸 在 sodium tetrahydroborate 、 氯化亚砜 、 六甲基二硅氧烷 、 TEA 、 sodium ethanolate 、 phosphorus pentoxide 、 臭氧 、 三乙胺 作用下， 以 四氯化碳 、 乙醇 、 二氯甲烷 为溶剂， 反应 75.75h， 生成 <1S-(1β,9β,9a-β)>-1-(Benzoyloxy)octahydro-9-hydroxy-4H-quinolizin-4-one
  参考文献：
  名称：

  Synthesis of Chiral Hydroxylated Quinolizidines via Vinylogous Bischler-Napieralski Nitrilium Ion Cyclizations

  摘要：

  Treatment of the amido esters 9 and 17 with PPSE (polyphosphoric acid trimethylsilyl ester) followed by NaBH4 in ethanol gave the quinolizidinones 11-14 and 19 via a vinylogous Bischler-Napieralski nitrilium ion cyclization-reductive lactamization two-step process. Subsequent ozonolysis and reduction afforded chiral hydroxylated quinolizidines in moderate to good yield. In contrast to five-membered-ring formation, six-membered-ring formation via nitrilium-ion cyclization requires a p-methoxy-substituted styryl terminator. The effect para-substituted styryl terminators have on the energy of activation and Delta H for the cyclization process has been calculated by semiempirical and ab initio methods.

  DOI：

  10.1021/jo00087a026

文献信息

• Radical cyclizations of acylsilanes in the synthesis of (+)-swainsonine and formal synthesis of (−)-epiquinamide
  作者：Ming-Jen Chen、Yeun-Min Tsai

  DOI：10.1016/j.tet.2010.12.048

  日期：2011.2

  form the indolizidine skeleton through a 1,6-cyclization. In the second approach, (S)-(+)-5-oxo-2-tetrahydrofurancarboxylic acid (23) was used to construct the same ring system through a 1,5-cyclization. Starting from acid 23, we also synthesized exo-1-hydroxyquinolizidin-4-one (56), which was a synthetic intermediate in the synthesis of polyhydroxylated quinolizidine (−)-epiquinamide.

  酰基硅烷的自由基环化是一种有用的合成方法。为了证明该方法以环化为关键步骤的多功能性，通过两种不同的键连接方法合成了多羟基化的吲哚并吡啶（+）-swainsonine，以构建双环骨架。在第一种方法中，我们使用2,3-异亚丙基d -ribono -1,4-内酯（20）作为手性结构单元，以形成通过1,6-环化的吲嗪啶骨架。在第二种方法中，使用（S）-（+）-5-氧代-2-四氢呋喃羧酸（23）通过1，5-环化反应构建相同的环系统。从酸23开始，我们还合成了exo -1-hydroxyquinolizidin-4-one（56），其是多羟基化喹oli嗪（-）-表喹酰胺的合成中的合成中间体。
• Synthesis of Chiral Hydroxylated Quinolizidines via Vinylogous Bischler-Napieralski Nitrilium Ion Cyclizations
  作者：Angela L. Marquart、Brent L. Podlogar、Edward W. Huber、David A. Demeter、Norton P. Peet、Herschel J. R. Weintraub、Michael R. Angelastro

  DOI：10.1021/jo00087a026

  日期：1994.4

  Treatment of the amido esters 9 and 17 with PPSE (polyphosphoric acid trimethylsilyl ester) followed by NaBH4 in ethanol gave the quinolizidinones 11-14 and 19 via a vinylogous Bischler-Napieralski nitrilium ion cyclization-reductive lactamization two-step process. Subsequent ozonolysis and reduction afforded chiral hydroxylated quinolizidines in moderate to good yield. In contrast to five-membered-ring formation, six-membered-ring formation via nitrilium-ion cyclization requires a p-methoxy-substituted styryl terminator. The effect para-substituted styryl terminators have on the energy of activation and Delta H for the cyclization process has been calculated by semiempirical and ab initio methods.