4-bromo-3-oxo-butyric acid (1S,2R)-1-diisopropylcarbamoyl-7,7-dimethyl-bicyclo[2.2.1]hept-2-yl ester | 1193319-99-1

• 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: 4-bromo-3-oxo-butyric acid (1S,2R)-1-diisopropylcarbamoyl-7,7-dimethyl-bicyclo[2.2.1]hept-2-yl ester
• CAS: 1193319-99-1
• 化学式: C₂₀H₃₂BrNO₄
• 分子量: 430.382
• InChiKey: VUEYEQHRDRNDNL-KKVAFCGZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.72
• 重原子数：
  26.0
• 可旋转键数：
  7.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  63.68
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  4-bromo-3-oxo-butyric acid (1S,2R)-1-diisopropylcarbamoyl-7,7-dimethyl-bicyclo[2.2.1]hept-2-yl ester 、 异戊烯醇 在 sodium hydride 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 0.5h， 以75%的产率得到4-(3-methyl-but-2-enyloxy)-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：

  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