cis-1-pivaloyloxy-3-indanol

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: cis-1-pivaloyloxy-3-indanol
• 英文别名: [(1R,3S)-3-hydroxy-2,3-dihydro-1H-inden-1-yl] 2,2-dimethylpropanoate
• 化学式: C₁₄H₁₈O₃
• 分子量: 234.295
• InChiKey: BFDDMSTUZXOWPM-NWDGAFQWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2,2-Dimethyl-thiopropionic acid S-((S)-4-tert-butyl-4,5-dihydro-thiazol-2-yl) ester 以 甲苯 为溶剂， 反应 14.0h， 生成 cis-1-pivaloyloxy-3-indanol
  参考文献：
  名称：

  Asymmetric Acylation of sec-Alcohols with Twisted Amides Possessing Axial Chirality Induced by the Adjacent Asymmetric Center

  摘要：

  This paper reports that axially chiral twisted amides serve as asymmetric acylating agents for sec-alcohols under neutral conditions. Kinetic resolution of various racemic sec-alcohols and desymmetrization of 1,2-, 1,3-, and 1,4-meso-diols were performed by using the twisted amides. The utility of this desymmetrization method was shown by the preparation of the synthetic intermediate 28 for macrolide antibiotic nodusmicin and 18-deoxynargenicin. The stereoselectivity of the acylation reactions is significantly dependent on the bulkiness of both the acyl group and the C-4 substituent of the chiral auxiliary. When an amide possessing an imidazolyl group at C-4 was employed, the stereoselectivity was reversed to give R esters. A possible working model of the acylation reaction is also described on the basis of the structural studies of the twisted amides by IR and H-1 and C-13 NMR spectroscopies and AM1 calculations. These studies suggested that rotamer II is thermodynamically more stable than the others. The rotamer II has an axial chirality about its C(O)-N linkage that is induced by the adjacent chiral center. This would enable discrimination of the two enantiomeric hydroxy groups of the racemic alcohols or meso-diols.

  DOI：

  10.1021/jo990892p

文献信息

• 10.1055/a-2322-0904
  作者：Ui, Ayano、Iwakura, Manaya、Yoshimatsu, Shuhei、Nakata, Kenya

  DOI：10.1055/a-2322-0904

  日期：——

  AbstractChiral guanidine-catalyzed desymmetrization of meso-indan-1,3-diols was achieved via enantioselective silylation by using chlorosilanes in good yields with high selectivity. The combination of chlorosilanes and catalysts was determined by the substituents at the C-2 position on the substrate. It was found that the fused phenyl ring on the substrate was essential for achieving high selectivity. The proposed method was found to be applicable to several types of substrates under optimized reaction conditions. Double silylative kinetic resolution with additive Horeau amplification was observed to establish high selectivity.
• Asymmetric Acylation of <i>s</i><i>ec</i>-Alcohols with Twisted Amides Possessing Axial Chirality Induced by the Adjacent Asymmetric Center
  作者：Shinji Yamada、Hiroko Katsumata

  DOI：10.1021/jo990892p

  日期：1999.12.1

  This paper reports that axially chiral twisted amides serve as asymmetric acylating agents for sec-alcohols under neutral conditions. Kinetic resolution of various racemic sec-alcohols and desymmetrization of 1,2-, 1,3-, and 1,4-meso-diols were performed by using the twisted amides. The utility of this desymmetrization method was shown by the preparation of the synthetic intermediate 28 for macrolide antibiotic nodusmicin and 18-deoxynargenicin. The stereoselectivity of the acylation reactions is significantly dependent on the bulkiness of both the acyl group and the C-4 substituent of the chiral auxiliary. When an amide possessing an imidazolyl group at C-4 was employed, the stereoselectivity was reversed to give R esters. A possible working model of the acylation reaction is also described on the basis of the structural studies of the twisted amides by IR and H-1 and C-13 NMR spectroscopies and AM1 calculations. These studies suggested that rotamer II is thermodynamically more stable than the others. The rotamer II has an axial chirality about its C(O)-N linkage that is induced by the adjacent chiral center. This would enable discrimination of the two enantiomeric hydroxy groups of the racemic alcohols or meso-diols.