N-(phenylseleno)ethyl-2α-(2',2'-dimethylvinyl)-4,4,7α-trimethyl-trans-octahydro-1,3-benzoxazine | 235093-69-3

• 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-(phenylseleno)ethyl-2α-(2',2'-dimethylvinyl)-4,4,7α-trimethyl-trans-octahydro-1,3-benzoxazine
• 英文别名: (2S,4aS,7R,8aR)-4,4,7-trimethyl-2-(2-methylprop-1-enyl)-3-(2-phenylselanylethyl)-4a,5,6,7,8,8a-hexahydro-2H-benzo[e][1,3]oxazine
• CAS: 235093-69-3
• 化学式: C₂₃H₃₅NOSe
• 分子量: 420.497
• InChiKey: KDMLJIKUELMPHI-NMIHRBCNSA-N

物化性质

• 沸点：
  476.1±45.0 °C(Predicted)

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-(phenylseleno)ethyl-2α-(2',2'-dimethylvinyl)-4,4,7α-trimethyl-trans-octahydro-1,3-benzoxazine 在 氢氧化钾 、 molecular sieve 、 偶氮二异丁腈 、 水 、 三正丁基氢锡 、 二异丁基氢化铝 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 甲苯 、 苯 为溶剂， 反应 4.25h， 生成 长叶薄荷酮
  参考文献：
  名称：

  A Novel Case of Diastereoselection in 5-exo Radical Cyclization Promoted by Hydrogen Bonding

  摘要：

  Moderate stereocontrol in 5-exo radical cyclizations of N,N-disubstituted (-)-8-amino menthol derivatives, promoted by tributyltin hydride and AIBN, was achieved. The stereoselection was explained in terms of hydrogen bond formation in the 1,3-amino alcohol derivative. The presence of one additional stereocenter at the allylic chain enhanced the stereoselection giving a single cyclization stereoisomer. The cyclization products were easily converted into enantiopure 5-alkyl- or 2,3-dialkyl-substituted pyrrolidines.

  DOI：

  10.1002/1099-0690(200011)2000:22<3727::aid-ejoc3727>3.0.co;2-c
• 作为产物：
  描述：

  Phenylselenoacetaldehyde 在 sodium tetrahydroborate 、 三氟化硼乙醚 作用下， 以 四氢呋喃 、 二氯甲烷 、 苯 为溶剂， 反应 98.0h， 生成 N-(phenylseleno)ethyl-2α-(2',2'-dimethylvinyl)-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.
• A Novel Case of Diastereoselection in 5-exo Radical Cyclization Promoted by Hydrogen Bonding
  作者：Rafael Pedrosa、Celia Andrés、Juan P. Duque-Soladana、Pilar Mendiguchía

  DOI：10.1002/1099-0690(200011)2000:22<3727::aid-ejoc3727>3.0.co;2-c

  日期：2000.11

  Moderate stereocontrol in 5-exo radical cyclizations of N,N-disubstituted (-)-8-amino menthol derivatives, promoted by tributyltin hydride and AIBN, was achieved. The stereoselection was explained in terms of hydrogen bond formation in the 1,3-amino alcohol derivative. The presence of one additional stereocenter at the allylic chain enhanced the stereoselection giving a single cyclization stereoisomer. The cyclization products were easily converted into enantiopure 5-alkyl- or 2,3-dialkyl-substituted pyrrolidines.