(2S,5R,6S,8R,9R)-5,6-diphenyl-7(S)-ethyl-8,9-dicarbomethoxy-1-aza-4-oxabicyclo<4.3.0>nonan-3-one | 144538-23-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: (2S,5R,6S,8R,9R)-5,6-diphenyl-7(S)-ethyl-8,9-dicarbomethoxy-1-aza-4-oxabicyclo<4.3.0>nonan-3-one
• 英文别名: dimethyl (3R,4S,6S,7S,8R,8aS)-6-ethyl-1-oxo-3,4-diphenyl-3,4,6,7,8,8a-hexahydropyrrolo[2,1-c][1,4]oxazine-7,8-dicarboxylate
• CAS: 144538-23-8
• 化学式: C₂₅H₂₇NO₆
• 分子量: 437.492
• InChiKey: WQYIZOVLRNJFAM-REGVOWLASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  32
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  82.1
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (2S,5R,6S,8R,9R)-5,6-diphenyl-7(S)-ethyl-8,9-dicarbomethoxy-1-aza-4-oxabicyclo<4.3.0>nonan-3-one 在 palladium dichloride 氢气 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 48.0h， 以93%的产率得到(2S,3R,4R,5S)-2-carboxy-3,4-dicarbomethoxy-5-ethylpyrrolidine
  参考文献：
  名称：

  Asymmetric [1,3]-dipolar cycloaddition reactions: synthesis of highly substituted proline derivatives

  摘要：

  The asymmetric [1,3]-dipolar cycloaddition reactions of azomethine ylides derived from (5R,6S)-2,3,5,6-tetrahydro-5,6-diphenyl-1,4-oxazin-2-one with various aldehydes and dimethyl maleate is described. The reactions prove to be highly endo-selective, installing three contiguous stereogenic centers in the newly formed five-membered ring with essentially complete stereochemical control. In the case of aldehydes higher than formaldehyde, a fourth stereogenic center is created; in most cases, poor stereoselectivity is observed at this center; the diastereomers formed in these cases can be separated by chromatography and separately converted into the amino acids. The bicyclic dipolar adducts can be cleaved with either catalytic hydrogenolysis or hydrolytic ring opening, esterification, and lead tetraacetate removal of the chiral auxiliary.

  DOI：

  10.1021/jo00050a029
• 作为产物：
  描述：

  (2R,3S)-(-)-N-Boc-2,3-二苯基-6-氧代吗啉 在 对甲苯磺酸 、 sodium sulfate 、 三乙胺 、 三氟乙酸 作用下， 以 苯 为溶剂， 反应 102.33h， 生成 (2S,5R,6S,8R,9R)-5,6-diphenyl-7(S)-ethyl-8,9-dicarbomethoxy-1-aza-4-oxabicyclo<4.3.0>nonan-3-one
  参考文献：
  名称：

  Asymmetric [1,3]-dipolar cycloaddition reactions: synthesis of highly substituted proline derivatives

  摘要：

  The asymmetric [1,3]-dipolar cycloaddition reactions of azomethine ylides derived from (5R,6S)-2,3,5,6-tetrahydro-5,6-diphenyl-1,4-oxazin-2-one with various aldehydes and dimethyl maleate is described. The reactions prove to be highly endo-selective, installing three contiguous stereogenic centers in the newly formed five-membered ring with essentially complete stereochemical control. In the case of aldehydes higher than formaldehyde, a fourth stereogenic center is created; in most cases, poor stereoselectivity is observed at this center; the diastereomers formed in these cases can be separated by chromatography and separately converted into the amino acids. The bicyclic dipolar adducts can be cleaved with either catalytic hydrogenolysis or hydrolytic ring opening, esterification, and lead tetraacetate removal of the chiral auxiliary.

  DOI：

  10.1021/jo00050a029

文献信息

• Asymmetric [1,3]-dipolar cycloaddition reactions: synthesis of highly substituted proline derivatives
  作者：Robert M. Williams、Weixu Zhai、David J. Aldous、Suzanne C. Aldous

  DOI：10.1021/jo00050a029

  日期：1992.11

  The asymmetric [1,3]-dipolar cycloaddition reactions of azomethine ylides derived from (5R,6S)-2,3,5,6-tetrahydro-5,6-diphenyl-1,4-oxazin-2-one with various aldehydes and dimethyl maleate is described. The reactions prove to be highly endo-selective, installing three contiguous stereogenic centers in the newly formed five-membered ring with essentially complete stereochemical control. In the case of aldehydes higher than formaldehyde, a fourth stereogenic center is created; in most cases, poor stereoselectivity is observed at this center; the diastereomers formed in these cases can be separated by chromatography and separately converted into the amino acids. The bicyclic dipolar adducts can be cleaved with either catalytic hydrogenolysis or hydrolytic ring opening, esterification, and lead tetraacetate removal of the chiral auxiliary.