(1R,2S,7R,7aS)-7-benzoyloxy-2-hydroxy-1-(methoxycarbonyl)hexahydropyrrolizin-3-one | 158146-78-2

• 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: (1R,2S,7R,7aS)-7-benzoyloxy-2-hydroxy-1-(methoxycarbonyl)hexahydropyrrolizin-3-one
• 英文别名: methyl (1R,2S,7R,8S)-7-benzoyloxy-2-hydroxy-3-oxo-1,2,5,6,7,8-hexahydropyrrolizine-1-carboxylate
• CAS: 158146-78-2
• 化学式: C₁₆H₁₇NO₆
• 分子量: 319.314
• InChiKey: QKGZHELRJBIBHD-LPWJVIDDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  23
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  93.1
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (S)-(+)-alpha-甲氧基苯乙酸 、 (1R,2S,7R,7aS)-7-benzoyloxy-2-hydroxy-1-(methoxycarbonyl)hexahydropyrrolizin-3-one 在 吡啶 、 N-cyclohexyl-N'-<(N''-methyl-2-morpholinio)ethyl>carbodiimide 4-toluenesulfonate 、 1-羟基苯并三唑 作用下， 以 乙腈 为溶剂， 反应 56.0h， 以58%的产率得到(1S,6R,6aS,7R)-1-<(S)-(Methoxyphenylacetyl)oxy>-6-(benzoyloxy)-7-carbomethoxyhexahydro-1H-pyrrolizin-2-one
  参考文献：
  名称：

  The Tandem Cycloaddition Chemistry of Nitroalkenes. A Novel Synthesis of (-)-Hastanecine

  摘要：

  A short and efficient asymmetric synthesis of the pyrrolizidine necine base (-)-hastanecine is described. The key reaction in the synthesis is a sequential inter [4+2]/inter[3+2] cycloaddition. The Lewis acid promoted [4+2] cycloaddition between 2-acyloxy nitroalkene 16 and chiral vinyl ether 17 afforded a nitronate which underwent facile [3+2] cycloaddition with dimethyl maleate. The resulting nitroso acetal 19 had all the required stereocenters for (-)-hastanecine. The critical unmasking of the nitroso acetal 19 employed a hydrogenolytic cleavage to give the 1-azabicyclo-[3.3.0]octane skeleton of (-)-hastanecine.

  DOI：

  10.1021/jo00098a027
• 作为产物：
  描述：

  (2R)-2-benzyloxy-1,4-bis(methanesulfonyloxy)butane 在 hexacarbonyl molybdenum 、 盐酸羟胺 、 三乙胺 、 mercury(II) oxide 作用下， 以 二氯甲烷 、 水 、 乙腈 、 苯 为溶剂， 反应 77.0h， 生成 (1R,2S,7R,7aS)-7-benzoyloxy-2-hydroxy-1-(methoxycarbonyl)hexahydropyrrolizin-3-one
  参考文献：
  名称：

  Cycloaddition of an Enantiopure Cyclic Nitrone to Maleate: Straightforward Synthesis of the Necine Base (-)-Hastanecine

  摘要：

  已报道了necine碱（-）-hastanecine（吡咯烷生物碱hastacine和punctanecine的亚基）的正式合成。关键中间体7由28.3%总产率的L-苹果酸衍生物二甲基酯11通过五个步骤合成。通过在二甲基酯11上进行Mitsunobu反应，获得了目标化合物C7的正确绝对立体化学。其余立体中心（C1和C7a）所需的立体化学来自硝酮9（通过完全位控获得）与马来酸二甲酯的关键环加成反应中高度优选的外消旋方法。

  DOI：

  10.1055/s-1997-3222

文献信息

• Cycloaddition of an Enantiopure Cyclic Nitrone to Maleate: Straightforward Synthesis of the Necine Base (-)-Hastanecine
  作者：Andrea Goti、Valentina Fedi、Luca Nannelli、Francesco De Sarlo、Alberto Brandi

  DOI：10.1055/s-1997-3222

  日期：1997.5

  A formal synthesis of the necine base (-)-hastanecine, subunit of the pyrrolizidine alkaloids hastacine and punctanecine, is reported. The key intermediate 7 is synthesized in five steps from dimesylate 11, derived from L-malic acid, in 28.3% overall yield. The correct absolute stereochemistry at C7 in the target compound is attained by means of a Mitsunobu reaction on dimesylate 11. The desired stereochemistry at the remaining stereogenic centres (C1 and C7a) derives from a highly preferential exo-anti approach in the key cycloaddition of nitrone 9 (obtained with complete regiocontrol) to dimethyl maleate.

  已报道了necine碱（-）-hastanecine（吡咯烷生物碱hastacine和punctanecine的亚基）的正式合成。关键中间体7由28.3%总产率的L-苹果酸衍生物二甲基酯11通过五个步骤合成。通过在二甲基酯11上进行Mitsunobu反应，获得了目标化合物C7的正确绝对立体化学。其余立体中心（C1和C7a）所需的立体化学来自硝酮9（通过完全位控获得）与马来酸二甲酯的关键环加成反应中高度优选的外消旋方法。
• The Tandem Cycloaddition Chemistry of Nitroalkenes. A Novel Synthesis of (-)-Hastanecine
  作者：Scott E. Denmark、Atli Thorarensen

  DOI：10.1021/jo00098a027

  日期：1994.9

  A short and efficient asymmetric synthesis of the pyrrolizidine necine base (-)-hastanecine is described. The key reaction in the synthesis is a sequential inter [4+2]/inter[3+2] cycloaddition. The Lewis acid promoted [4+2] cycloaddition between 2-acyloxy nitroalkene 16 and chiral vinyl ether 17 afforded a nitronate which underwent facile [3+2] cycloaddition with dimethyl maleate. The resulting nitroso acetal 19 had all the required stereocenters for (-)-hastanecine. The critical unmasking of the nitroso acetal 19 employed a hydrogenolytic cleavage to give the 1-azabicyclo-[3.3.0]octane skeleton of (-)-hastanecine.
• Goti, Andrea; Cicchi, Stefano; Cacciarini, Martina, European Journal of Organic Chemistry, 2000, # 21, p. 3633 - 3645
  作者：Goti, Andrea、Cicchi, Stefano、Cacciarini, Martina、Cardona, Francesca、Fedi, Valentina、Brandi, Alberto

  DOI：——

  日期：——