N-crotyl-2α-(phenylseleno)methyl-4,4,7α-trimethyl-trans-octahydro-1,3-benzoxazine | 235093-82-0

• 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-crotyl-2α-(phenylseleno)methyl-4,4,7α-trimethyl-trans-octahydro-1,3-benzoxazine
• 英文别名: (2S,4aS,7R,8aR)-3-[(E)-but-2-enyl]-4,4,7-trimethyl-2-(phenylselanylmethyl)-4a,5,6,7,8,8a-hexahydro-2H-benzo[e][1,3]oxazine
• CAS: 235093-82-0
• 化学式: C₂₂H₃₃NOSe
• 分子量: 406.47
• InChiKey: QYDSDSRDOYJWBA-KWDHTBBFSA-N

物化性质

• 沸点：
  461.7±41.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.25
• 重原子数：
  25
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.64
• 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-crotyl-2α-(phenylseleno)methyl-4,4,7α-trimethyl-trans-octahydro-1,3-benzoxazine 在 lithium aluminium tetrahydride 、 三氯化铝 、 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 0.17h， 生成 (3'R)-8-(3'-ethylpyrrolidinyl)menthol
  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-crotyl-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