(-)-ent-Darlingine | 58471-10-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 环庚吡喃类
• 英文名称: (-)-ent-Darlingine
• 英文别名: (+)-darlingine；darlingine；(5S)-2,3,10-trimethyl-6,7,8,9-tetrahydro-5H-5,8-epiazano-cyclohepta[b]pyran-4-one；Darlingin；(1S,9R)-4,5,12-trimethyl-6-oxa-12-azatricyclo[7.2.1.02,7]dodeca-2(7),4-dien-3-one
• CAS: 58471-10-6
• 化学式: C₁₃H₁₇NO₂
• 分子量: 219.283
• InChiKey: WBTZDCUVPGAROE-ZJUUUORDSA-N

物化性质

• 熔点：
  162-5°C

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  tigloyl cyanide 在 正丁基锂 、 sodium carbonate 、 (R)-(-)-N-新戊基-1-苯基-2-(1-吡啶烷)乙胺 、 lithium chloride 、 copper(ll) bromide 作用下， 以 乙酸乙酯 为溶剂， 反应 34.0h， 生成 (-)-ent-Darlingine
  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

• Tropane alkaloids from Darlingia darlingiana
  作者：Peter L. Katavic、Mark S. Butler、Ronald J. Quinn、Paul I. Forster、Gordon P. Guymer

  DOI：10.1016/s0031-9422(99)00263-0

  日期：1999.10

  A new gamma-pyranotropane, darlingine N-oxide, was isolated from the bark and leaves of Darlingia darlingiana, along with the known compound, darlingine. 1D-NOESY NMR experiments indicated that the N-methyl groups of both alkaloids were orientated towards the pyran ring. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Synthesis of Tropane Alkaloids via Enantioselective Deprotonation of Tropinone
  作者：Marek Majewski、Ryszard Lazny

  DOI：10.1021/jo00123a018

  日期：1995.9

  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.