(3R,3aS,4aR,6R,8aS)-3-Benzyl-6,9,9-trimethyl-decahydro-benzo[e]pyrrolo[2,1-b][1,3]oxazine | 235093-75-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (3R,3aS,4aR,6R,8aS)-3-Benzyl-6,9,9-trimethyl-decahydro-benzo[e]pyrrolo[2,1-b][1,3]oxazine
• 英文别名: (1R,3S,4R,9S,12R)-4-benzyl-8,8,12-trimethyl-2-oxa-7-azatricyclo[7.4.0.03,7]tridecane
• CAS: 235093-75-1
• 化学式: C₂₁H₃₁NO
• 分子量: 313.483
• InChiKey: CUIRHATYYWYVSU-JUSBFGHESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.71
• 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：

  (3R,3aS,4aR,6R,8aS)-3-Benzyl-6,9,9-trimethyl-decahydro-benzo[e]pyrrolo[2,1-b][1,3]oxazine 在 氢氧化钾 、 lithium aluminium tetrahydride 、 三氯化铝 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 为溶剂， 反应 4.17h， 生成 ((R)-3-Benzyl-pyrrolidin-1-yl)-phenyl-methanone
  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 sodium tetrahydroborate 、 偶氮二异丁腈 、 三氟化硼乙醚 、 氢气 、 三正丁基氢锡 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 苯 为溶剂， 25.0 ℃ 、1.01 MPa 条件下， 反应 122.0h， 生成 (3R,3aS,4aR,6R,8aS)-3-Benzyl-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

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.