4-bromo-benzoic acid (S)-3-benzyloxy-4-oxo-3-vinyl-cyclopentylmethyl ester | 1019842-64-8

• 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: 4-bromo-benzoic acid (S)-3-benzyloxy-4-oxo-3-vinyl-cyclopentylmethyl ester
• CAS: 1019842-64-8
• 化学式: C₂₂H₂₁BrO₄
• 分子量: 429.31
• InChiKey: SYNGLVSJNAZSBF-VGSWGCGISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.73
• 重原子数：
  27.0
• 可旋转键数：
  7.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为产物：
  描述：

  4-bromo-benzoic acid 3-(1-benzyloxy-propa-1,2-dienyl)-3-hydroxy-cyclobutylmethyl ester 在 (dibenzylideneacetone)3palladium⁽⁰⁾ monochloroform complex 、 (R,R)-anthracene ligand 4 A molecular sieve 、 三乙胺 、 苯甲酸 作用下， 以 二氯甲烷 、 1,2-二氯乙烷 为溶剂， 反应 6.0h， 生成 4-bromo-benzoic acid (S)-3-benzyloxy-4-oxo-3-vinyl-cyclopentylmethyl ester 、 4-bromo-benzoic acid (S)-3-benzyloxy-4-oxo-3-vinyl-cyclopentylmethyl ester 、 4-bromo-benzoic acid (S)-3-benzyloxy-4-oxo-3-vinyl-cyclopentylmethyl ester
  参考文献：
  名称：

  Palladium-Catalyzed Diastereo- and Enantioselective Wagner−Meerwein Shift: Control of Absolute Stereochemistry in the C−C Bond Migration Event

  摘要：

  Inducing absolute stereochemistry in Wagner-Meerwein shifts was examined in a ring expansion protocol. Initiated by generation of a pi-allylpalladium intermediate by hydropalladation of allenes, the ring expansion of allenylcyclobutanol substrates proceeded with excellent diastereo- and enantioselectivities. The results demonstrate that, during the C-C bond migration process, our chiral catalysts can control the stereochemistry of both the pi-allylpalladium intermediate and the corresponding migration bond. Moreover, the stereochemical outcome of the reaction can be rationalized very well with the working model of the chiral catalyst. The method provides an efficient way to synthesize highly substituted cyclopentanones with an alpha-chiral O-tertiary center which has various synthetic applications.

  DOI：

  10.1021/ja7111299