(1S,4R)-2-[(3'R,4'R,5'S,6'R)-5'-methylbicyclo[2.2.1]heptene-4'-carbonyl]-4,7,7-trimethyl-2-azabicyclo[2.2.1]-5-hepten-3-one | 344800-88-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: (1S,4R)-2-[(3'R,4'R,5'S,6'R)-5'-methylbicyclo[2.2.1]heptene-4'-carbonyl]-4,7,7-trimethyl-2-azabicyclo[2.2.1]-5-hepten-3-one
• 英文别名: (1S,4R)-4,7,7-trimethyl-2-[(1R,2R,3S,4S)-3-methylbicyclo[2.2.1]hept-5-ene-2-carbonyl]-2-azabicyclo[2.2.1]hept-5-en-3-one
• CAS: 344800-88-0
• 化学式: C₁₈H₂₃NO₂
• 分子量: 285.386
• InChiKey: ZWPNGMARGCPTTA-CUOQVMEYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  21
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  37.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1S,4R)-2-[(3'R,4'R,5'S,6'R)-5'-methylbicyclo[2.2.1]heptene-4'-carbonyl]-4,7,7-trimethyl-2-azabicyclo[2.2.1]-5-hepten-3-one 在 palladium on activated charcoal 氢气 作用下， 以 乙醇 为溶剂， 以100%的产率得到
  参考文献：
  名称：

  Toward the development of a general chiral auxiliary. Part 6: Structural effects on diastereoselection using camphor derived lactams: evaluation of (1R,4S)-1,7,7-trimethyl-3-azabicyclo[2.2.1]hept-5-en-3-one as a chiral controller

  摘要：

  A new camphor-derived chiral lactam was designed, prepared and evaluated as a chiral controller in asymmetric Diels-Alder and aldol reactions. The new lactam, bearing a C(5)C(6) double bond, was anticipated to afford higher diastereofacial selection resulting from the removal of additional steric hindrance to reagent approach distal to the geminal dimethyl bridge by comparison with the previously studied saturated analogue (the favored mode approach in the saturated analogue). Surprisingly, a deterioration in the extent of diastereofacial selectivity was observed for both reaction types. These results are interpreted in terms of the geometric changes imposed upon the ring system as a whole by introduction of the unsaturation. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00013-1
• 作为产物：
  描述：

  (1R)-1,2,2-trimethylcyclopent-3-ene-1-carboxylic acid 在 正丁基锂 、 氯化亚砜 、 potassium tert-butylate 、 溴 、 三甲基铝 、 sodium hexamethyldisilazane 、 甲基二氯化铝 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 1,2-二氯乙烷 为溶剂， 反应 56.5h， 生成 (1S,4R)-2-[(3'R,4'R,5'S,6'R)-5'-methylbicyclo[2.2.1]heptene-4'-carbonyl]-4,7,7-trimethyl-2-azabicyclo[2.2.1]-5-hepten-3-one
  参考文献：
  名称：

  Toward the development of a general chiral auxiliary. Part 6: Structural effects on diastereoselection using camphor derived lactams: evaluation of (1R,4S)-1,7,7-trimethyl-3-azabicyclo[2.2.1]hept-5-en-3-one as a chiral controller

  摘要：

  A new camphor-derived chiral lactam was designed, prepared and evaluated as a chiral controller in asymmetric Diels-Alder and aldol reactions. The new lactam, bearing a C(5)C(6) double bond, was anticipated to afford higher diastereofacial selection resulting from the removal of additional steric hindrance to reagent approach distal to the geminal dimethyl bridge by comparison with the previously studied saturated analogue (the favored mode approach in the saturated analogue). Surprisingly, a deterioration in the extent of diastereofacial selectivity was observed for both reaction types. These results are interpreted in terms of the geometric changes imposed upon the ring system as a whole by introduction of the unsaturation. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00013-1

文献信息

• Toward the development of a general chiral auxiliary. Part 6: Structural effects on diastereoselection using camphor derived lactams: evaluation of (1R,4S)-1,7,7-trimethyl-3-azabicyclo[2.2.1]hept-5-en-3-one as a chiral controller
  作者：Robert K. Boeckman、Michelle A. Laci、Alan T. Johnson

  DOI：10.1016/s0957-4166(01)00013-1

  日期：2001.2

  A new camphor-derived chiral lactam was designed, prepared and evaluated as a chiral controller in asymmetric Diels-Alder and aldol reactions. The new lactam, bearing a C(5)C(6) double bond, was anticipated to afford higher diastereofacial selection resulting from the removal of additional steric hindrance to reagent approach distal to the geminal dimethyl bridge by comparison with the previously studied saturated analogue (the favored mode approach in the saturated analogue). Surprisingly, a deterioration in the extent of diastereofacial selectivity was observed for both reaction types. These results are interpreted in terms of the geometric changes imposed upon the ring system as a whole by introduction of the unsaturation. (C) 2001 Elsevier Science Ltd. All rights reserved.