(R)-4-((tert-butyldiphenylsilyl)oxy)-2-hydroxy-3,3-dimethylbutanoic acid

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (R)-4-((tert-butyldiphenylsilyl)oxy)-2-hydroxy-3,3-dimethylbutanoic acid
• 英文别名: (2R)-4-[tert-butyl(diphenyl)silyl]oxy-2-hydroxy-3,3-dimethylbutanoic acid
• 化学式: C₂₂H₃₀O₄Si
• 分子量: 386.563
• InChiKey: AZDQJNONKJYGJG-IBGZPJMESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.03
• 重原子数：
  27
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  66.8
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (R)-4-((tert-butyldiphenylsilyl)oxy)-2-hydroxy-3,3-dimethylbutanoic acid 在 2-氮杂金刚烷-N-氧自由基 、 sodium nitrite 作用下， 以 aq. phosphate buffer 、 水 、 乙腈 为溶剂， 反应 2.0h， 以87%的产率得到4-((tert-butyldiphenylsilyl)oxy)-3,3-dimethyl-2-oxobutanoic acid
  参考文献：
  名称：

  硝基氧自由基催化的好氧氧化使α-羟基酸选择性转化为α-酮酸

  摘要：

  描述了由2-氮杂金刚烷N-氧基（AZADO）（一种硝基氧基自由基催化剂）催化的α-羟基酸到α-酮酸的化学选择性氧化。尽管α-酮酸不稳定并且可以在氧化条件下轻易释放CO 2，但是使用分子氧作为助氧化剂可以实现所需的化学选择性氧化。

  DOI：

  10.1021/acs.orglett.6b01964
• 作为产物：
  描述：

  (R)-4-((tert-butyldiphenylsilyl)oxy)-3,3-dimethylbutane-1,2-diol 在 2,2,6,6-四甲基哌啶氧化物 、 sodium hypochlorite 、 sodium chlorite 作用下， 以 aq. phosphate buffer 、 甲苯 为溶剂， 反应 4.0h， 以88%的产率得到(R)-4-((tert-butyldiphenylsilyl)oxy)-2-hydroxy-3,3-dimethylbutanoic acid
  参考文献：
  名称：

  Chemoselective Catalytic Oxidation of 1,2-Diols to α-Hydroxy Acids Controlled by TEMPO–ClO₂ Charge-Transfer Complex

  摘要：

  Chemoselective catalytic oxidation from 1,2-diols to a-hydroxy acids in a cat. TEMPO/cat. NaOCl/NaClO2 system has been achieved. The use of a two-phase condition consisting of hydrophobic toluene and water suppresses the concomitant oxidative cleavage. A study of the mechanism suggests that the observed selectivity is derived from the precise solubility: control of diols and hydroxy acids as well as the active species Of TEMPO, Although the oxoammonium species TEMPO+Cl- is hydrophilic, the active species dissolves into the organic layer by the formation of the charge-transfer (CT) complex TEMPO-ClO2 under the reaction conditions.

  DOI：

  10.1021/acs.orglett.5b01003

文献信息

• Chemoselective Catalytic Oxidation of 1,2-Diols to α-Hydroxy Acids Controlled by TEMPO–ClO₂ Charge-Transfer Complex
  作者：Keisuke Furukawa、Masatoshi Shibuya、Yoshihiko Yamamoto

  DOI：10.1021/acs.orglett.5b01003

  日期：2015.5.1

  Chemoselective catalytic oxidation from 1,2-diols to a-hydroxy acids in a cat. TEMPO/cat. NaOCl/NaClO2 system has been achieved. The use of a two-phase condition consisting of hydrophobic toluene and water suppresses the concomitant oxidative cleavage. A study of the mechanism suggests that the observed selectivity is derived from the precise solubility: control of diols and hydroxy acids as well as the active species Of TEMPO, Although the oxoammonium species TEMPO+Cl- is hydrophilic, the active species dissolves into the organic layer by the formation of the charge-transfer (CT) complex TEMPO-ClO2 under the reaction conditions.
• Chemoselective Conversion from α-Hydroxy Acids to α-Keto Acids Enabled by Nitroxyl-Radical-Catalyzed Aerobic Oxidation
  作者：Keisuke Furukawa、Haruki Inada、Masatoshi Shibuya、Yoshihiko Yamamoto

  DOI：10.1021/acs.orglett.6b01964

  日期：2016.9.2

  The chemoselective oxidation of α-hydroxy acids to α-keto acids catalyzed by 2-azaadamantane N-oxyl (AZADO), a nitroxyl radical catalyst, is described. Although α-keto acids are labile and can easily release CO2 under oxidation conditions, the use of molecular oxygen as a cooxidant enables the desired chemoselective oxidation.

  描述了由2-氮杂金刚烷N-氧基（AZADO）（一种硝基氧基自由基催化剂）催化的α-羟基酸到α-酮酸的化学选择性氧化。尽管α-酮酸不稳定并且可以在氧化条件下轻易释放CO 2，但是使用分子氧作为助氧化剂可以实现所需的化学选择性氧化。