methyl (S)-α-hydroxy-α-biphenylyl-acetate | 73586-08-0

• 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: methyl (S)-α-hydroxy-α-biphenylyl-acetate
• 英文别名: (-)-methyl 2-hydroxy-2-(4-biphenyl)acetate；methyl (2S)-2-hydroxy-2-(4-phenylphenyl)acetate
• CAS: 73586-08-0
• 化学式: C₁₅H₁₄O₃
• 分子量: 242.274
• InChiKey: WGYKXUHWRAQYAW-AWEZNQCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl (S)-α-hydroxy-α-biphenylyl-acetate 、 叔丁基二甲基氯硅烷 在 咪唑 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 Methyl (S)-(+)-α-(1,1'-biphenyl-4-yl)-α-<<(1,1-dimethylethyl)dimethylsilyl>oxy>acetate
  参考文献：
  名称：

  Synthesis of Enantiomerically Pure Stereogenically Labile 4-Aryl-2-hydroxytetronic Acids from Enantiomerically Pure Silyl-Protected Mandelaldehydes: aci-Reductone Analogs of Propionic Acid Nonsteroidal Anti-inflammatory Agents

  摘要：

  Enantiomerically pure 4-aryl-2-hydroxytetronic acids (3) are expected to be useful tools for determining the mechanism by which corresponding racemic aci-reductones produce their multiple biological effects. Our published synthetic methods for the construction of the title compounds were only useful for the preparation of 4-alkyl analogues owing to facile racemization of the chiral benzylic proton with 4-aryl systems. The synthesis of these enantiomerically pure 4-aryl aci-reductones has now been accomplished in four steps by condensing enantiomerically pure tert-butyldimethylsilyl protected mandelaldehydes 16a-c with the anion of ethyl 1,3-dithiane-2-carboxylate in the presence of pivaloyl chloride to yield protected beta,gamma-dihydroxy-alpha-ketobutanoates 22a-c after dithiane hydrolysis. Reaction of 22a-c with tetrabutylammonium fluoride :resulted in silyl deprotection, cyclization, and pivaloyl migration to afford 2-(pivaloyloxy)tetronic acids 25a-c. Pivaloate deprotection by either acid hydrolysis or selective hydride reduction produced enantiopure targets 3a-c.

  DOI：

  10.1021/jo00116a015
• 作为产物：
  描述：

  2-氧代-2-(4-苯基苯基)乙酸 在 C₄₈H₅₀N₂O₂P₂Ru*2C₁₈H₁₅P*4Cl^(1-)*2Ru⁽²⁺⁾ 、 氢气 、 sodium acetate 、 potassium carbonate 、 三苯基膦 作用下， 以 甲醇 、 丙酮 为溶剂， 反应 24.0h， 生成 methyl (S)-α-hydroxy-α-biphenylyl-acetate
  参考文献：
  名称：

  RuPHOX-Ru催化不对称加氢合成手性α-芳基α-羟基羧酸

  摘要：

  已成功开发了钌烯基膦基-恶唑啉-钌络合物（RuPHOX-Ru）催化的α-芳基酮酸不对称氢化反应，可提供高收率和ee高达97％的相应手性α-芳基α-羟基羧酸。该反应可以在相对较低的催化剂负载量（至多5000 S / C）下以克为单位进行，所得产物可以转化为几种手性结构单元，生物活性化合物和手性药物。

  DOI：

  10.1002/adsc.201700846

文献信息

• Efficient syntheses for optically pure stereogenically labile 4-substituted-2-hydroxytetronic acids
  作者：Donald T. Witiak、Ashok K. Tehim

  DOI：10.1021/jo00290a059

  日期：1990.2
• Catalytic Asymmetric Reaction with Water: Enantioselective Synthesis of α-Hydroxyesters by a Copper–Carbenoid OH Insertion Reaction
  作者：Shou-Fei Zhu、Chao Chen、Yan Cai、Qi-Lin Zhou

  DOI：10.1002/anie.200704651

  日期：2008.1.18
• OPTICALLY PURE 4-ARYL-2-HYDROXYTETRONIC ACIDS
  申请人：THE OHIO STATE UNIVERSITY RESEARCH FOUNDATION

  公开号：EP0746551B1

  公开（公告）日：2002-09-04
• The Synthesis of Chiral α-Aryl α-Hydroxy Carboxylic Acids via RuPHOX-Ru Catalyzed Asymmetric Hydrogenation
  作者：Huan Guo、Jing Li、Delong Liu、Wanbin Zhang

  DOI：10.1002/adsc.201700846

  日期：2017.10.25

  A ruthenocenyl phosphino‐oxazoline‐ruthenium complex (RuPHOX−Ru) catalyzed asymmetric hydrogenation of α‐aryl keto acids has been successfully developed, affording the corresponding chiral α‐aryl α‐hydroxy carboxylic acids in high yields and with up to 97% ee. The reaction could be performed on a gram scale with a relatively low catalyst loading (up to 5000 S/C) and the resulting products can be transformed

  已成功开发了钌烯基膦基-恶唑啉-钌络合物（RuPHOX-Ru）催化的α-芳基酮酸不对称氢化反应，可提供高收率和ee高达97％的相应手性α-芳基α-羟基羧酸。该反应可以在相对较低的催化剂负载量（至多5000 S / C）下以克为单位进行，所得产物可以转化为几种手性结构单元，生物活性化合物和手性药物。
• Synthesis of Enantiomerically Pure Stereogenically Labile 4-Aryl-2-hydroxytetronic Acids from Enantiomerically Pure Silyl-Protected Mandelaldehydes: aci-Reductone Analogs of Propionic Acid Nonsteroidal Anti-inflammatory Agents
  作者：Allen T. Hopper、Donald T. Witiak

  DOI：10.1021/jo00116a015

  日期：1995.6

  Enantiomerically pure 4-aryl-2-hydroxytetronic acids (3) are expected to be useful tools for determining the mechanism by which corresponding racemic aci-reductones produce their multiple biological effects. Our published synthetic methods for the construction of the title compounds were only useful for the preparation of 4-alkyl analogues owing to facile racemization of the chiral benzylic proton with 4-aryl systems. The synthesis of these enantiomerically pure 4-aryl aci-reductones has now been accomplished in four steps by condensing enantiomerically pure tert-butyldimethylsilyl protected mandelaldehydes 16a-c with the anion of ethyl 1,3-dithiane-2-carboxylate in the presence of pivaloyl chloride to yield protected beta,gamma-dihydroxy-alpha-ketobutanoates 22a-c after dithiane hydrolysis. Reaction of 22a-c with tetrabutylammonium fluoride :resulted in silyl deprotection, cyclization, and pivaloyl migration to afford 2-(pivaloyloxy)tetronic acids 25a-c. Pivaloate deprotection by either acid hydrolysis or selective hydride reduction produced enantiopure targets 3a-c.