(1S,6S,8aS)-octahydro-1-acetoxy-6-indolizine | 132317-05-6

• 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: (1S,6S,8aS)-octahydro-1-acetoxy-6-indolizine
• 英文别名: (1S,6S,8aS)-octahydro-1-acetoxy-6-[N-benzyl-N-(benzyloxycarbonyl)amino]indolizine；[(1S,6S,8aS)-6-[benzyl(phenylmethoxycarbonyl)amino]-1,2,3,5,6,7,8,8a-octahydroindolizin-1-yl] acetate
• CAS: 132317-05-6
• 化学式: C₂₅H₃₀N₂O₄
• 分子量: 422.524
• InChiKey: GTPRZKFFBUOLFE-HJOGWXRNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.99
• 重原子数：
  31.0
• 可旋转键数：
  6.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  59.08
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  (1S,6S,8aS)-octahydro-1-acetoxy-6-indolizine 在 palladium on activated charcoal 氢气 作用下， 以 乙醇 为溶剂， 反应 4.0h， 以78%的产率得到流涎胺
  参考文献：
  名称：

  Synthesis of (-)-slaframine and related indolizidines

  摘要：

  An enantioselective synthesis of the indolizidine alkaloid (-)-slaframine 1 is reported. Reductive double cyclization of the azido epoxy tosylate 48 afforded the indolizidine 52, which was converted to (-)-slaframine in two steps. The cyclization substrate 48 was prepared in optically pure form from L-glutamic acid. A similar sequence starting with the epoxide 49 allowed the synthesis of (-)-1,8a-diepislaframine 56. Other routes to slaframine were investigated, often using an intramolecular cycloaddition of an azide with an alkene as a key step. Although these routes did not produce slaframine, they illustrated novel and efficient methods for the assembly of the indolizidine skeleton. Cyclization of the azidodiene 20 afforded the indolizidine 21 in one step as a single diastereomer, presumably a result of a chairlike transition state in the initial dipolar cycloaddition. Desulfurization and deprotection produced (-)-8a-epidesacetoxyslaframine 27. Cyclopropylimine rearrangement of 30 gave the indolizidine 31, which was also converted into (-)-8a-epidesacetoxyslaframine 27. Dipolar cycloaddition of 38 gave the 1-pyrroline 39, which was converted to the indolizidine 40 in one operation using Evans' double alkylation of the 1-metalloenamine derivative of 40. Attempted oxidation of 40 to the ketone 41 was unsuccessful, precluding a reductive amination approach to slaframine.

  DOI：

  10.1021/jo00040a045
• 作为产物：
  描述：

  (S)-n-苄基谷氨酸 在 palladium on activated charcoal 吡啶 、 盐酸 、 4-二甲氨基吡啶 、 硼烷四氢呋喃络合物 、 草酰氯 、 叠氮磷酸二苯酯 、 四丁基氟化铵 、 氢气 、 碳酸氢钠 、 potassium carbonate 、 二甲基亚砜 、 三乙胺 、 间氯过氧苯甲酸 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 水 为溶剂， -78.0~23.0 ℃ 、101.33 kPa 条件下， 反应 195.0h， 生成 (1S,6S,8aS)-octahydro-1-acetoxy-6-indolizine
  参考文献：
  名称：

  A synthesis of (-)-slaframine and (-)-1,8a-diepislaframine

  摘要：

  Reductive cyclization of the optically pure azido epoxides 12 and 13 afforded the indolizidines 14 and 16, which were conveted into (-)-slaframine 1 and (-)-1,8a-diepislaframine 18.

  DOI：

  10.1021/jo00006a002

文献信息

• A synthesis of (-)-slaframine and (-)-1,8a-diepislaframine
  作者：William H. Pearson、Stephen C. Bergmeier

  DOI：10.1021/jo00006a002

  日期：1991.3

  Reductive cyclization of the optically pure azido epoxides 12 and 13 afforded the indolizidines 14 and 16, which were conveted into (-)-slaframine 1 and (-)-1,8a-diepislaframine 18.
• Synthesis of (-)-slaframine and related indolizidines
  作者：William H. Pearson、Stephen C. Bergmeier、John P. Williams

  DOI：10.1021/jo00040a045

  日期：1992.7

  An enantioselective synthesis of the indolizidine alkaloid (-)-slaframine 1 is reported. Reductive double cyclization of the azido epoxy tosylate 48 afforded the indolizidine 52, which was converted to (-)-slaframine in two steps. The cyclization substrate 48 was prepared in optically pure form from L-glutamic acid. A similar sequence starting with the epoxide 49 allowed the synthesis of (-)-1,8a-diepislaframine 56. Other routes to slaframine were investigated, often using an intramolecular cycloaddition of an azide with an alkene as a key step. Although these routes did not produce slaframine, they illustrated novel and efficient methods for the assembly of the indolizidine skeleton. Cyclization of the azidodiene 20 afforded the indolizidine 21 in one step as a single diastereomer, presumably a result of a chairlike transition state in the initial dipolar cycloaddition. Desulfurization and deprotection produced (-)-8a-epidesacetoxyslaframine 27. Cyclopropylimine rearrangement of 30 gave the indolizidine 31, which was also converted into (-)-8a-epidesacetoxyslaframine 27. Dipolar cycloaddition of 38 gave the 1-pyrroline 39, which was converted to the indolizidine 40 in one operation using Evans' double alkylation of the 1-metalloenamine derivative of 40. Attempted oxidation of 40 to the ketone 41 was unsuccessful, precluding a reductive amination approach to slaframine.