(4aR,5S,6R)-N-(3-Bromopropionyl)-5,6-epoxy-2,3-dihydro-4H,7H-10a-(benzyloxycarbonyl)quinoline | 171523-79-8

• 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: (4aR,5S,6R)-N-(3-Bromopropionyl)-5,6-epoxy-2,3-dihydro-4H,7H-10a-(benzyloxycarbonyl)quinoline
• 英文别名: benzyl (1aR,7aS,7bS)-4-(3-bromopropanoyl)-1a,2,5,6,7,7b-hexahydrooxireno[2,3-f]quinoline-7a-carboxylate
• CAS: 171523-79-8
• 化学式: C₂₀H₂₂BrNO₄
• 分子量: 420.303
• InChiKey: SQYLSIQHZBEVHI-ZTNFWEORSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  59.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (4aR,5S,6R)-N-(3-Bromopropionyl)-5,6-epoxy-2,3-dihydro-4H,7H-10a-(benzyloxycarbonyl)quinoline 在 n-butyl tin hydride 、 偶氮二异丁腈 作用下， 以 苯 为溶剂， 生成 (7aS,8S,9R,11aS)-1,2,5,6,10,11-Hexahydro-7H-3-oxo-7a-(benzyloxycarbonyl)-8,9-epoxypyrrolo<2,1-j>quinoline 、 (7aS,9R,10S,10aR)-2,3,6,7,7a,10b-Hexahydro-1H,8H-5-oxo-9,10-epoxy-10a-(benzyloxycarbonyl)benzoquinolizine
  参考文献：
  名称：

  Asymmetric Organic Synthesis. Radical Cyclizations of Chiral Enamides

  摘要：

  Stereoselective radical cyclizations to the enamide double bond have excellent potential for utilization in alkaloid and related nitrogen heterocycle synthesis. Complete facial selectivity has been found for radical cyclizations of chiral substrates 1a --> 2, 7 --> 8, 11 --> 12 + 13, 15 --> 16 + 17, and 19 --> 20. The stereoselectivity for reduction of the intermediate tertiary radicals with Bu(3)SnH correlates with product stability. For example, 7 gives cis-dihydro 8 with no trace of the trans-dihydro isomer 9, 3.6 kcal/mol less stable than 8. Radical cyclization of 11 gave a 1:1 mixture of the six-membered ring lactam 12 and the spirocyclic lactam 13. Diastereomers 12 and 14 have near equivalent stabilities, but radical reduction from the beta-face is blocked by the presence of the adjacent benzyloxycarbonyl substituent. The formation of 20 from 19, by way of a disfavored 5-endo-trig cyclization pathway may have value as a model for synthesis of kopsinine-type alkaloids. The conversion of 8 to the functionalized hexahydrojulolidine 23 also is described.

  DOI：

  10.1021/jo00129a052
• 作为产物：
  描述：

  (4aR,5R,6R)-5-Iodo-2,3,7,8-tetrahydro-4H-quinoline-4a,6-carbolactone 在 正丁基锂 、 碳酸氢钠 作用下， 以 四氢呋喃 为溶剂， 反应 2.75h， 生成 (4aR,5S,6R)-N-(3-Bromopropionyl)-5,6-epoxy-2,3-dihydro-4H,7H-10a-(benzyloxycarbonyl)quinoline
  参考文献：
  名称：

  Asymmetric Organic Synthesis. Radical Cyclizations of Chiral Enamides

  摘要：

  Stereoselective radical cyclizations to the enamide double bond have excellent potential for utilization in alkaloid and related nitrogen heterocycle synthesis. Complete facial selectivity has been found for radical cyclizations of chiral substrates 1a --> 2, 7 --> 8, 11 --> 12 + 13, 15 --> 16 + 17, and 19 --> 20. The stereoselectivity for reduction of the intermediate tertiary radicals with Bu(3)SnH correlates with product stability. For example, 7 gives cis-dihydro 8 with no trace of the trans-dihydro isomer 9, 3.6 kcal/mol less stable than 8. Radical cyclization of 11 gave a 1:1 mixture of the six-membered ring lactam 12 and the spirocyclic lactam 13. Diastereomers 12 and 14 have near equivalent stabilities, but radical reduction from the beta-face is blocked by the presence of the adjacent benzyloxycarbonyl substituent. The formation of 20 from 19, by way of a disfavored 5-endo-trig cyclization pathway may have value as a model for synthesis of kopsinine-type alkaloids. The conversion of 8 to the functionalized hexahydrojulolidine 23 also is described.

  DOI：

  10.1021/jo00129a052

文献信息

• Asymmetric Organic Synthesis. Radical Cyclizations of Chiral Enamides
  作者：Arthur G. Schultz、Peter R. Guzzo、Deanne M. Nowak

  DOI：10.1021/jo00129a052

  日期：1995.12

  Stereoselective radical cyclizations to the enamide double bond have excellent potential for utilization in alkaloid and related nitrogen heterocycle synthesis. Complete facial selectivity has been found for radical cyclizations of chiral substrates 1a --> 2, 7 --> 8, 11 --> 12 + 13, 15 --> 16 + 17, and 19 --> 20. The stereoselectivity for reduction of the intermediate tertiary radicals with Bu(3)SnH correlates with product stability. For example, 7 gives cis-dihydro 8 with no trace of the trans-dihydro isomer 9, 3.6 kcal/mol less stable than 8. Radical cyclization of 11 gave a 1:1 mixture of the six-membered ring lactam 12 and the spirocyclic lactam 13. Diastereomers 12 and 14 have near equivalent stabilities, but radical reduction from the beta-face is blocked by the presence of the adjacent benzyloxycarbonyl substituent. The formation of 20 from 19, by way of a disfavored 5-endo-trig cyclization pathway may have value as a model for synthesis of kopsinine-type alkaloids. The conversion of 8 to the functionalized hexahydrojulolidine 23 also is described.