(6S,8aR)-octahydro-6-aminoindolizine | 132256-88-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚里西啶
• 英文名称: (6S,8aR)-octahydro-6-aminoindolizine
• 英文别名: (-)-8-epi-1-desacetoxyslaframine；(-)-8a-Epidesacetoxyslaframine；8a-epi-desacetoxyslaframine；(6S,8AS)-octahydroindolizin-6-amine；(6S,8aS)-1,2,3,5,6,7,8,8a-octahydroindolizin-6-amine
• CAS: 132256-88-3
• 化学式: C₈H₁₆N₂
• 分子量: 140.228
• InChiKey: DPBJLNMVJTYHJR-YUMQZZPRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  29.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  Boc-L-脯氨酸甲酯 在 palladium on activated charcoal 正丁基锂 、 氢气 、 二异丁基氢化铝 作用下， 以 甲醇 、 甲苯 为溶剂， -78.0~270.0 ℃ 、399.97 Pa 条件下， 反应 6.0h， 生成 (6S,8aR)-octahydro-6-aminoindolizine
  参考文献：
  名称：

  A novel thermolytic annulation of an oxazolidinone: an enantiospecific synthesis of (-)-slaframine

  摘要：

  Optically pure beta-aminopiperidines can be prepared in high yields through a thermolytic annulation sequence involving ring opening of an oxazolidinone.

  DOI：

  10.1021/jo00042a002

文献信息

• Synthesis of indolidines by the 1,3-dipolar cycloaddition of azides with methylenecyclopropanes followed by cyclopropyumine rearrangement
  作者：Philip C. Heidt.‡、Stephen C. Bergmeier†、WilliAm H. Pearson‡

  DOI：10.1016/s0040-4039(00)97867-5

  日期：1990.1

  Cyclic imines 6a and 6b were obtained by the intramolecular 1,3-dipolar cycloaddition of azides with methylenecyclopropanes. Acid catalyzed rearrangement produced bicyclic (−)-enamines 7, which upon reduction provided indoilizidenes 8. A similar strategy was used for the synthesis of (−)-8a-epi-desacctoxyslaframine 16.

  通过叠氮化物的分子内1，3-偶极环加成与亚甲基环丙烷获得环亚胺6a和6b。酸催化的重排产生了双环（-）-烯胺7，还原后提供了indoilizidenes 8。类似的策略被用于合成（-）-8a-epi-desacctoxyslaframine 16。
• 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.
• A novel thermolytic annulation of an oxazolidinone: an enantiospecific synthesis of (-)-slaframine
  作者：Mukund P. Sibi、James W. Christensen、Biqin Li、Paul A. Renhowe

  DOI：10.1021/jo00042a002

  日期：1992.7

  Optically pure beta-aminopiperidines can be prepared in high yields through a thermolytic annulation sequence involving ring opening of an oxazolidinone.
• HEIDT, PHILIP C.;BERGMEIER, STEPHEN C.;PEARSON, WILLIAM H., TETRAHEDRON LETT., 31,(1990) N8, C. 5441-5444
  作者：HEIDT, PHILIP C.、BERGMEIER, STEPHEN C.、PEARSON, WILLIAM H.

  DOI：——

  日期：——
• Enantiospecific Synthesis of (−)-Slaframine and Related Hydroxylated Indolizidines. Utilization of a Nucleophilic Alaninol Synthon Derived from Serine¹
  作者：Mukund P. Sibi、James W. Christensen

  DOI：10.1021/jo9908546

  日期：1999.8.1

  A general methodology for the synthesis of indolizidine alkaloids delta-coniceine (12), 1-hydroxyindolizidine (20), desacetoxy slaframine (24), slaframine (34), and an analogue (37) has been developed. This convergent approach utilizes the available chirality in proline and serine and is conceptually different from other approaches. A highly stereoselective coupling of the prolinals with a nucleophilic alaninol synthon provides the precursors for the key cyclization. A novel thermolytic annulation of an oxazolidinone is the key step in the formation of the six-membered piperidine ring. Further elaboration provides the target natural products 24, 34, and 37 in good overall yields.