(3S,7R,7aR)-7-Benzo[1,3]dioxol-5-yl-3-phenyl-tetrahydro-pyrrolo[2,1-b]oxazol-5-one | 145549-04-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并间二氧杂环戊烯类
• 英文名称: (3S,7R,7aR)-7-Benzo[1,3]dioxol-5-yl-3-phenyl-tetrahydro-pyrrolo[2,1-b]oxazol-5-one
• 英文别名: (3S,7R,7aR)-7-(1,3-benzodioxol-5-yl)-3-phenyl-3,6,7,7a-tetrahydro-2H-pyrrolo[2,1-b][1,3]oxazol-5-one
• CAS: 145549-04-8
• 化学式: C₁₉H₁₇NO₄
• 分子量: 323.348
• InChiKey: BUNMZQVZPKVCIQ-SPYBWZPUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  24
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  48
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (3S,7R,7aR)-7-Benzo[1,3]dioxol-5-yl-3-phenyl-tetrahydro-pyrrolo[2,1-b]oxazol-5-one 在 lithium aluminium tetrahydride 、 三氯化铝 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以90%的产率得到(2S)-2-[(3R)-3-(1,3-benzodioxol-5-yl)pyrrolidin-1-yl]-2-phenylethanol
  参考文献：
  名称：

  The synthesis of aracemic 4-substituted pyrrolidinones and 3-substituted pyrrolidines. An asymmetric synthesis of (-)-rolipram

  摘要：

  Conjugate additions of RCuCNLi to the chiral alpha,beta-unsaturated lactam 4 gives almost exclusive exo addition-a reversal in stereochemistry when cuprates were added to chiral lactam 1. The lactams 5 were transformed into 4-substituted pyrrolidinones 8 via a three-step sequence which involved decarbalkoxylation, silane reduction and metal-ammonia benzylamine cleavage. The chemical yields as well as the enantiomeric purity were very high for this process. As an example of the usefulness of this scheme, the antidepressant (-)-Rolipram was prepared in good overall yield. Furthermore, the bicyclic lactams 6 were readily transformed, using alane as the reducing agent, to 3-substituted pyrrolidines 11. Absolute configurations of 8 and 11 were confirmed by comparison with literature assignments which also gave strong support to the facial addition of the cuprates to 4.

  DOI：

  10.1021/jo00053a012
• 作为产物：
  描述：

  (3S,7aR)-5-Oxo-3-phenyl-hexahydro-pyrrolo[2,1-b]oxazole-6-carboxylic acid benzyl ester 在 palladium on activated charcoal 苯基溴化硒 、 双氧水 、 ammonium formate 作用下， 反应 4.5h， 生成 (3S,7R,7aR)-7-Benzo[1,3]dioxol-5-yl-3-phenyl-tetrahydro-pyrrolo[2,1-b]oxazol-5-one
  参考文献：
  名称：

  The synthesis of aracemic 4-substituted pyrrolidinones and 3-substituted pyrrolidines. An asymmetric synthesis of (-)-rolipram

  摘要：

  Conjugate additions of RCuCNLi to the chiral alpha,beta-unsaturated lactam 4 gives almost exclusive exo addition-a reversal in stereochemistry when cuprates were added to chiral lactam 1. The lactams 5 were transformed into 4-substituted pyrrolidinones 8 via a three-step sequence which involved decarbalkoxylation, silane reduction and metal-ammonia benzylamine cleavage. The chemical yields as well as the enantiomeric purity were very high for this process. As an example of the usefulness of this scheme, the antidepressant (-)-Rolipram was prepared in good overall yield. Furthermore, the bicyclic lactams 6 were readily transformed, using alane as the reducing agent, to 3-substituted pyrrolidines 11. Absolute configurations of 8 and 11 were confirmed by comparison with literature assignments which also gave strong support to the facial addition of the cuprates to 4.

  DOI：

  10.1021/jo00053a012

文献信息

• The synthesis of aracemic 4-substituted pyrrolidinones and 3-substituted pyrrolidines. An asymmetric synthesis of (-)-rolipram
  作者：A. I. Meyers、Lawrence Snyder

  DOI：10.1021/jo00053a012

  日期：1993.1

  Conjugate additions of RCuCNLi to the chiral alpha,beta-unsaturated lactam 4 gives almost exclusive exo addition-a reversal in stereochemistry when cuprates were added to chiral lactam 1. The lactams 5 were transformed into 4-substituted pyrrolidinones 8 via a three-step sequence which involved decarbalkoxylation, silane reduction and metal-ammonia benzylamine cleavage. The chemical yields as well as the enantiomeric purity were very high for this process. As an example of the usefulness of this scheme, the antidepressant (-)-Rolipram was prepared in good overall yield. Furthermore, the bicyclic lactams 6 were readily transformed, using alane as the reducing agent, to 3-substituted pyrrolidines 11. Absolute configurations of 8 and 11 were confirmed by comparison with literature assignments which also gave strong support to the facial addition of the cuprates to 4.