3-oxo-butyric acid (1S,2R)-1-diisopropylcarbamoyl-7,7-dimethyl-bicyclo[2.2.1]hept-2-yl ester | 1193319-98-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 3-oxo-butyric acid (1S,2R)-1-diisopropylcarbamoyl-7,7-dimethyl-bicyclo[2.2.1]hept-2-yl ester
• 英文别名: [(1S,2R,4R)-1-[di(propan-2-yl)carbamoyl]-7,7-dimethyl-2-bicyclo[2.2.1]heptanyl] 3-oxobutanoate
• CAS: 1193319-98-0
• 化学式: C₂₀H₃₃NO₄
• 分子量: 351.486
• InChiKey: NNZKXPKCXWNAJF-QINHECLXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  25
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  63.7
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3-oxo-butyric acid (1S,2R)-1-diisopropylcarbamoyl-7,7-dimethyl-bicyclo[2.2.1]hept-2-yl ester 在 溴 作用下， 以 氯仿 为溶剂， 反应 16.5h， 以88%的产率得到4-bromo-3-oxo-butyric acid (1S,2R)-1-diisopropylcarbamoyl-7,7-dimethyl-bicyclo[2.2.1]hept-2-yl ester
  参考文献：
  名称：

  Asymmetric [2,3]-Wittig rearrangement of the dienolates of chiral secondary alcohol-substituted β-pyrrolidinyl-γ-allyloxyl-α,β-unsaturated esters: total synthesis of (+)-eldanolide

  摘要：

  The asymmetric [2,3]-Wittig rearrangement of the dienolates of various chiral beta-pyrrolidinyl-gamma-allyloxyl-alpha,beta-unsaturated esters was investigated using different chiral secondary alcohol Substitutions. When (1S,2R,4R)-2-hydroxy-7,7-dimethylbicyclo[2,2,1]heptane-1-carboxylic acid diisopropylamide was used as chiral auxiliary, it provided the best enantioselectivity in the rearrangement. When various gamma-allyloxy substitutions underwent temperature and additive studies, 1,1-dimethylpropenoxy substitution was found to give the best enantioselectivity. The methodology was applied to the total synthesis of eldanolide. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2009.07.028
• 作为产物：
  描述：

  丙二酸环(亚)异丙酯 、 (1S,2R,4R)-2-Hydroxy-7,7-dimethyl-bicyclo[2.2.1]heptane-1-carboxylic acid diisopropylamide 以 5,5-dimethyl-1,3-cyclohexadiene 为溶剂， 反应 3.0h， 以94%的产率得到3-oxo-butyric acid (1S,2R)-1-diisopropylcarbamoyl-7,7-dimethyl-bicyclo[2.2.1]hept-2-yl ester
  参考文献：
  名称：

  Asymmetric [2,3]-Wittig rearrangement of the dienolates of chiral secondary alcohol-substituted β-pyrrolidinyl-γ-allyloxyl-α,β-unsaturated esters: total synthesis of (+)-eldanolide

  摘要：

  The asymmetric [2,3]-Wittig rearrangement of the dienolates of various chiral beta-pyrrolidinyl-gamma-allyloxyl-alpha,beta-unsaturated esters was investigated using different chiral secondary alcohol Substitutions. When (1S,2R,4R)-2-hydroxy-7,7-dimethylbicyclo[2,2,1]heptane-1-carboxylic acid diisopropylamide was used as chiral auxiliary, it provided the best enantioselectivity in the rearrangement. When various gamma-allyloxy substitutions underwent temperature and additive studies, 1,1-dimethylpropenoxy substitution was found to give the best enantioselectivity. The methodology was applied to the total synthesis of eldanolide. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2009.07.028

文献信息

• Asymmetric [2,3]-Wittig rearrangement of the dienolates of chiral secondary alcohol-substituted β-pyrrolidinyl-γ-allyloxyl-α,β-unsaturated esters: total synthesis of (+)-eldanolide
  作者：Yu-Jang Li、Guo-Ming Ho、Pin-Zu Chen

  DOI：10.1016/j.tetasy.2009.07.028

  日期：2009.8

  The asymmetric [2,3]-Wittig rearrangement of the dienolates of various chiral beta-pyrrolidinyl-gamma-allyloxyl-alpha,beta-unsaturated esters was investigated using different chiral secondary alcohol Substitutions. When (1S,2R,4R)-2-hydroxy-7,7-dimethylbicyclo[2,2,1]heptane-1-carboxylic acid diisopropylamide was used as chiral auxiliary, it provided the best enantioselectivity in the rearrangement. When various gamma-allyloxy substitutions underwent temperature and additive studies, 1,1-dimethylpropenoxy substitution was found to give the best enantioselectivity. The methodology was applied to the total synthesis of eldanolide. (C) 2009 Elsevier Ltd. All rights reserved.