(R)-diethyl 2-hydroxy-2-[1,2,3,4-tetrahydro-1-oxonaphthalen-2-yl]malonate

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 英文名称: (R)-diethyl 2-hydroxy-2-[1,2,3,4-tetrahydro-1-oxonaphthalen-2-yl]malonate
• 英文别名: diethyl 2-hydroxy-2-[(2R)-1-oxo-3,4-dihydro-2H-naphthalen-2-yl]propanedioate
• 化学式: C₁₇H₂₀O₆
• 分子量: 320.342
• InChiKey: XCNWXGJSCRNCIL-ZDUSSCGKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  23
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  89.9
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  (3,4-二氢-1-萘氧基)三甲基硅烷 、 酮基丙二酸二乙酯 在 C₄₃H₆₈CuF₆N₂O₉S₂Si₂ 、 六氟异丙醇 作用下， 以 乙醚 为溶剂， 反应 49.0h， 以89%的产率得到(R)-diethyl 2-hydroxy-2-[1,2,3,4-tetrahydro-1-oxonaphthalen-2-yl]malonate
  参考文献：
  名称：

  Enantioselective Mukaiyama-Aldol Reaction between Enol Silanes and Ketomalonate Catalyzed by the Copper(II) Complex of TIPS-Substituted Bis-oxazoline

  摘要：

  The stable complex [(4'S,5'S)-4b/Cu(Tf)(2)/H2O] (5), obtained from TIPS-Box and Copper triflate, catalyzes enantioselectively the Mukaiyama-aldol reactions between two silyl enol ethers (1a,b) and diethyl ketomalonate (2). Yields are very good and the ee of (R)-3b is up to 94%. When the reaction was catalyzed by 4-Ph-Box complex [(4'R)-4a/Cu(Tf)(2)], in which the configuration at the C-4 centre is opposite to that of 5, the same enantiomer was obtained. The undistorted square pyramidal structure of complex 5, determined by crystallographic structure, and the effect of water and molecular sieves on efficiency and selectivity of the catalyst, suggest some proposals to rationalize the resulting stereoselectivity.

  DOI：

  10.3987/com-12-s(n)11

文献信息

• Catalytic enantioselective addition of enol silanes to ketomalonate mediated by C2-symmetric bisoxazoline Lewis acid complexes
  作者：Frank Reichel、Xiangming Fang、Sulan Yao、Marina Ricci、Karl Anker Jørgensen

  DOI：10.1039/a902227i

  日期：——

  A catalytic enantioselective addition reaction of silyl enol ethers to ketomalonate in the presence of C2-symmetric copper(II) bisoxazolines as catalysts is presented; the reaction has been studied for different ligands and substrates under various reaction conditions and proceeds in good yield and with ee’s >90% and a procedure for the preparation of an optically active hydroxy acid is shown.

  本文介绍了一种在C2对称铜(II)双恶唑啉催化剂存在下，硅醚烯醇的催化不对称加成反应到酮丙二酸酯的过程；在不同反应条件下，对多种配体和底物进行了研究，反应收率良好，对映体过量率(ee)超过90%，并展示了一种制备光学活性羟基酸的方法。
• Enantioselective Mukaiyama-Aldol Reaction between Enol Silanes and Ketomalonate Catalyzed by the Copper(II) Complex of TIPS-Substituted Bis-oxazoline
  作者：Giovanni Desimoni、Guiseppe Faita、Alessandro Livieri、Laura Ponta

  DOI：10.3987/com-12-s(n)11

  日期：——

  The stable complex [(4'S,5'S)-4b/Cu(Tf)(2)/H2O] (5), obtained from TIPS-Box and Copper triflate, catalyzes enantioselectively the Mukaiyama-aldol reactions between two silyl enol ethers (1a,b) and diethyl ketomalonate (2). Yields are very good and the ee of (R)-3b is up to 94%. When the reaction was catalyzed by 4-Ph-Box complex [(4'R)-4a/Cu(Tf)(2)], in which the configuration at the C-4 centre is opposite to that of 5, the same enantiomer was obtained. The undistorted square pyramidal structure of complex 5, determined by crystallographic structure, and the effect of water and molecular sieves on efficiency and selectivity of the catalyst, suggest some proposals to rationalize the resulting stereoselectivity.