2-(phenylseleno)methylperhydro-1,3-benzoxazine | 235093-64-8

• 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: 2-(phenylseleno)methylperhydro-1,3-benzoxazine
• 英文别名: (2S,4aS,7R,8aR)-4,4,7-trimethyl-2-(phenylselanylmethyl)-2,3,4a,5,6,7,8,8a-octahydrobenzo[e][1,3]oxazine
• CAS: 235093-64-8
• 化学式: C₁₈H₂₇NOSe
• 分子量: 352.378
• InChiKey: REKLBUVVRXTGCJ-DZUCGIPZSA-N

物化性质

• 沸点：
  426.3±41.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.96
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  21.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(phenylseleno)methylperhydro-1,3-benzoxazine 在 sodium tetrahydroborate 、 三氟化硼乙醚 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 80.0h， 生成 N-(phenylseleno)ethyl-4,4,7α-trimethyl-2α-vinyl-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
• 作为产物：
  描述：

  (1R,2S,5R)-5-methyl-2-<1-methyl-1-(benzylamino)ethyl>cyclohexan-1-ol 在 palladium on activated charcoal 氢气 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 25.0 ℃ 、1.01 MPa 条件下， 反应 42.0h， 生成 2-(phenylseleno)methylperhydro-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

• A Novel Approach to Chiral, Nonracemic Pyrrolidines by 5-exo-trig Diastereoselective Radical Cyclization on Acrylamides Derived from (−)-8-Aminomenthol
  作者：Celia Andrés、Juan P. Duque-Soladana、Rafael Pedrosa

  DOI：10.1021/jo981693t

  日期：1999.6.1

  alpha,beta-Unsaturated amides supported on perhydro-1,3-benzoxazines derived from (-)-8-aminomenthol as chiral auxiliaries undergo regio- and stereoselective 5-exo-trig radical cyclization leading to diastereomeric five-membered lactams. These cyclization products are transformed into enantiopure 3,4-disubstituted pyrrolidines by reduction with aluminum hydride followed by removal of the menthol appendage.
• Diastereoselective 5-exo-trig radical cyclisation on N-Acryloyl-tetrahydro-1,3-oxazines. A novel approach to enantiopure 3-substituted pyrrolidines
  作者：Celia Andrés、J.Pablo Duque-Soladana、Jesús M. Iglesias、Rafael Pedrosa

  DOI：10.1016/s0040-4039(96)02091-6

  日期：1996.12

  N-Acryloyl-2-(phenylselenomethyl)-tetrahydro-1,3-oxazine 1 generates a carbon-centred radical in the presence of tri-n-butyltin hydride and AIBN. This radical underwent diastereoselective 5-exo-trig cyclisation leading to a mixture of five-membered lactams 2a and 2b (d.e. 68%). Chromatographic separation of the diastereomers and elimination of the chiral auxiliary provided enantiopure (R)-3-methylpyrrolidine in good chemical yield. Copyright (C) 1996 Elsevier Science Ltd
• 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.