N-prenyl-2α-(phenylseleno)methyl-4,4,7α-trimethyl-trans-octahydro-1,3-benzoxazine | 235093-84-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并恶嗪类
• 英文名称: N-prenyl-2α-(phenylseleno)methyl-4,4,7α-trimethyl-trans-octahydro-1,3-benzoxazine
• 英文别名: (2S,4aS,7R,8aR)-4,4,7-trimethyl-3-(3-methylbut-2-enyl)-2-(phenylselanylmethyl)-4a,5,6,7,8,8a-hexahydro-2H-benzo[e][1,3]oxazine
• CAS: 235093-84-2
• 化学式: C₂₃H₃₅NOSe
• 分子量: 420.497
• InChiKey: QNPVVCHVWDLNPW-NMIHRBCNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.64
• 重原子数：
  26
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-prenyl-2α-(phenylseleno)methyl-4,4,7α-trimethyl-trans-octahydro-1,3-benzoxazine 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 苯 为溶剂， 生成 (2S,3aS,4aR,6R,8aS)-2-Isopropyl-6,9,9-trimethyl-decahydro-benzo[e]pyrrolo[2,1-b][1,3]oxazine 、 (2R,3aS,4aR,6R,8aS)-2-Isopropyl-6,9,9-trimethyl-decahydro-benzo[e]pyrrolo[2,1-b][1,3]oxazine
  参考文献：
  名称：

  Regio- and Stereoselective 5-exo Radical Cyclizations on a Chiral Perhydro-1,3-benzoxazine Moiety. An Access to Enantiopure 3-Alkylpyrrolidines

  摘要：

  Both enantiomers of chiral, nonracemic S-alkyl-substituted pyrolidines are prepared by diastereoselective 5-exo-trig cyclization on (-)-8-aminomenthol-derived perhydro-1,3-benzoxazines used as chiral auxiliaries, followed by elimination of the menthol appendage. The diastereoselective radical cyclization is promoted by tributyltin hydride and occurs on a 3-aza-5-hexenyl-type radical, leading to five-membered rings in high yield. The stereocontrol of the cyclization is strongly influenced by 1,3-allylic strain so that an appropriate substitution pattern on the olefin-acceptor and the presence of a vicinal stereocenter are crucial for achieving good diastereoselectivity. The enantiopure pyrrolidines are obtained in three steps with concomitant recovering of the starting (+)-pulegone auxiliary.

  DOI：

  10.1021/jo9816921
• 作为产物：
  描述：

  Phenylselenoacetaldehyde 在 potassium carbonate 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 66.0h， 生成 N-prenyl-2α-(phenylseleno)methyl-4,4,7α-trimethyl-trans-octahydro-1,3-benzoxazine
  参考文献：
  名称：

  Regio- and Stereoselective 5-exo Radical Cyclizations on a Chiral Perhydro-1,3-benzoxazine Moiety. An Access to Enantiopure 3-Alkylpyrrolidines

  摘要：

  Both enantiomers of chiral, nonracemic S-alkyl-substituted pyrolidines are prepared by diastereoselective 5-exo-trig cyclization on (-)-8-aminomenthol-derived perhydro-1,3-benzoxazines used as chiral auxiliaries, followed by elimination of the menthol appendage. The diastereoselective radical cyclization is promoted by tributyltin hydride and occurs on a 3-aza-5-hexenyl-type radical, leading to five-membered rings in high yield. The stereocontrol of the cyclization is strongly influenced by 1,3-allylic strain so that an appropriate substitution pattern on the olefin-acceptor and the presence of a vicinal stereocenter are crucial for achieving good diastereoselectivity. The enantiopure pyrrolidines are obtained in three steps with concomitant recovering of the starting (+)-pulegone auxiliary.

  DOI：

  10.1021/jo9816921

文献信息

• Regio- and Stereoselective 5-<i>exo</i> Radical Cyclizations on a Chiral Perhydro-1,3-benzoxazine Moiety. An Access to Enantiopure 3-Alkylpyrrolidines
  作者：Celia Andrés、Juan P. Duque-Soladana、Rafael Pedrosa

  DOI：10.1021/jo9816921

  日期：1999.6.1

  Both enantiomers of chiral, nonracemic S-alkyl-substituted pyrolidines are prepared by diastereoselective 5-exo-trig cyclization on (-)-8-aminomenthol-derived perhydro-1,3-benzoxazines used as chiral auxiliaries, followed by elimination of the menthol appendage. The diastereoselective radical cyclization is promoted by tributyltin hydride and occurs on a 3-aza-5-hexenyl-type radical, leading to five-membered rings in high yield. The stereocontrol of the cyclization is strongly influenced by 1,3-allylic strain so that an appropriate substitution pattern on the olefin-acceptor and the presence of a vicinal stereocenter are crucial for achieving good diastereoselectivity. The enantiopure pyrrolidines are obtained in three steps with concomitant recovering of the starting (+)-pulegone auxiliary.