methyl 2-hydroxy-3-oxo-2-phenylbutanoate

• 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 2-hydroxy-3-oxo-2-phenylbutanoate
• 英文别名: (RS)-methyl 2-hydroxy-3-oxo-2-phenylbutanoate；Acetylmandelsauremethylester
• 化学式: C₁₁H₁₂O₄
• 分子量: 208.214
• InChiKey: PZMDAQFDPXTBQA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  63.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  苯甲酰甲酸甲酯 、 2,3-丁二酮 在 3-苄基羟乙基甲基噻唑氯化锂 、 三乙胺 作用下， 以 PEG₄₀₀ 为溶剂， 以51%的产率得到methyl 2-hydroxy-3-oxo-2-phenylbutanoate
  参考文献：
  名称：

  α-Diketones as acyl anion equivalents: a non-enzymatic thiamine-promoted route to aldehyde–ketone coupling in PEG400 as recyclable medium

  摘要：

  By mimicking the peculiar behavior of thiamine diphosphate-dependent acetylacetoin synthase, it has been demonstrated that thiamine hydrochloride 2a and its simple analogue thiazolium salt 2b are able to activate alpha-diketones as acyl anion equivalents in nucleophilic acylations, such as the homo-coupling of alpha-diketones and the hitherto unreported cross-coupling between a-diketones and alpha-ketoesters. These carboligation reactions were optimized under stoichiometric (2a) and catalytic conditions (2b) by using eco-friendly PEG400 as the reaction medium, thus allowing both solvent and thiazolium salt recycling. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.08.056

文献信息

• Efficient synthesis of α-hydroxy-β-ketoesters from methyl phenylglyoxalate and acid chlorides mediated by titanium trichloride
  作者：Silvia Araneo、Angelo Clerici、Ombretta Porta

  DOI：10.1016/s0040-4039(00)76800-6

  日期：1994.4

  Methyl phenylglyoxalate and acid chlorides undergo rapid condensation reactions on treatment with a TiCl3-THF/CH2Cl2 solution, in the presence of pyridine, at room temperature.

  在室温下，在吡啶存在下，用TiCl 3 -THF / CH 2 Cl 2溶液处理时，苯乙二醛草酸甲酯和酰氯会发生快速缩合反应。
• Acylation of a transient Ti(IV)-enolate by acyl halides and anhydrides. Facile synthesis of α-hydroxy-β-ketoesters
  作者：Angelo Clerici、Laura Clerici、Ombretta Porta

  DOI：10.1016/0040-4020(96)00621-7

  日期：1996.8

  Regioselective C-acylation at the carbonyl carbon of methyl phenylglyoxylate 1 occurs by reaction with a variety of acyl halides 3 and anhydrides 4 in the presence of TiCl3/py system in THF at room temperature. α-Hydroxy-β-ketoesters 5 are the only reaction products and pyridine is essential to obtain useful yields (50–90%). The mechanism of acylation involves the intermediacy of a nucleophilic a Ti(IV)-ene

  在室温下，在THF中，在TiCl 3 / py体系存在下，通过与各种酰基卤3和酸酐4反应，发生了苯基乙醛酸甲酯1的羰基碳上的区域选择性C-酰化反应。α-羟基-β-酮酸酯5是唯一的反应产物，吡啶对于获得有用的收率（50-90％）是必不可少的。酰化的机理涉及亲核的Ti（IV）-烯二醇盐B的中介。
• Tandem Oxidation/Rearrangement of β-Ketoesters to Tartronic Esters with Molecular Oxygen Catalyzed by Calcium Iodide under Visible Light Irradiation with Fluorescent Lamp
  作者：Naohiko Kanai、Hiroki Nakayama、Norihiro Tada、Akichika Itoh

  DOI：10.1021/ol1003675

  日期：2010.5.7

  It was found that β-ketoesters were directly transformed to the corresponding α-hydroxymalonic esters, tartronic esters, with molecular oxygen catalyzed by calcium iodide under visible light irradiation from fluorescent lamp. This reaction includes tandem oxidation/rearrangement and has received much attention from the viewpoint of reduction of energy consumption, labor, and solvents.

  发现在荧光灯的可见光照射下，碘化钙催化的分子氧将β-酮酸酯直接转化为相应的α-羟基丙二酸酯，tartronic酯。该反应包括串联氧化/重排，并且从减少能耗，劳力和溶剂的角度出发已经引起了广泛的关注。
• HYDROXYLATION OF BETA-DICARBONYLS WITH ZIRCONIUM CATALYSTS
  申请人：CASALNUOVO ALBERT LOREN

  公开号：US20080306259A1

  公开（公告）日：2008-12-11

  The present invention pertains to a process for preparing a compound of Formula I that is achiral, racemic or enantiomerically enriched at the hydroxylation center indicated by * comprising contacting a compound of Formula II with an oxidant selected from oxygen, hydrogen peroxide, peracids or alkyl hydropetoxides in the presence of a zirconium complex, wherein R 1 , R 2 and R 3 are as defined in the disclosure. This invention also pertains to zirconium complexes useful in this procedure comprising zirconium and a ligand of Formula III or its enantiomer wherein J, R 6 and n are as defined in the disclosure. This invention further pertains to a compound of Formula III or its enantiomer.

  本发明涉及一种制备公式I化合物的方法，该化合物是在羟基化中心处无手性、外消旋或对映富集的，所述方法包括将公式II化合物与氧、过氧化氢、过酸或烷基过氧化物等氧化剂在锆配合物的存在下接触，其中R1、R2和R3如本文所定义。本发明还涉及在该过程中有用的锆配合物，其包括锆和公式III配体或其对映体，其中J、R6和n如本文所定义。本发明还涉及公式III或其对映体的化合物。
• Hydroxylation of Beta-Dicarbonyls with Zirconium Catalysts
  申请人：Casalnuovo Albert Loren

  公开号：US20100185014A1

  公开（公告）日：2010-07-22

  The present invention pertains to a process for preparing a compound of Formula I that is achiral, racemic or enantiomerically enriched at the hydroxylation center indicated by * comprising contacting a compound of Formula II with an oxidant selected from oxygen, hydrogen peroxide, peracids or alkyl hydroperoxides in the presence of a zirconium complex, wherein R 1 , R 2 and R 3 are as defined in the disclosure. This invention also pertains to zirconium complexes useful in this procedure comprising zirconium and a ligand of Formula III or its enantiomer wherein J, R 6 and n are as defined in the disclosure. This invention further pertains to a compound of Formula III or its enantiomer.

  本发明涉及一种制备公式I化合物的方法，该化合物是在*处的羟基化中心上是无手性、外消旋或对映富集的，包括将公式II化合物与氧气、过氧化氢、过酸或烷基过氧化物等氧化剂在锆配合物存在下接触，其中R1、R2和R3如本文所定义。本发明还涉及在该过程中有用的锆配合物，包括锆和公式III或其对映体的配体，其中J、R6和n如本文所定义。本发明还涉及公式III或其对映体的化合物。