methyl 2-hydroxy-4-oxo-2-phenylpentanoate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: methyl 2-hydroxy-4-oxo-2-phenylpentanoate
• 英文别名: 2-hydroxy-4-oxo-2-phenyl-pentanoic acid methyl ester；methyl (2S)-2-hydroxy-4-oxo-2-phenylpentanoate
• 化学式: C₁₂H₁₄O₄
• 分子量: 222.241
• InChiKey: HAEVARUTAGRKQK-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 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 、 丙酮 在 2,2'-(1E,1'E)-(1R,2R)-cyclohexane-1,2-diylbis(azan-1-yl-1-ylidene)bis(methan-1-yl-1-ylidene)diquinolin-8-ol 、 溶剂黄146 作用下， 反应 72.0h， 以85%的产率得到methyl 2-hydroxy-4-oxo-2-phenylpentanoate
  参考文献：
  名称：

  原位形成的双功能伯胺-亚胺催化剂，用于α-酮基酯的不对称羟醛反应

  摘要：

  在最佳条件下：手性二亚胺前体的水解可通过布朗斯台德酸进行，形成原位伯胺-亚胺中间体，作为双官能伯氨基催化剂，从而促进α-酮酯与酮之间的直接不对称醛醇缩合反应。产率（高达88％）并且具有优异的对映选择性（参见方案； R 1，R 2，R 4＝烷基； R 3＝芳基）。

  DOI：

  10.1002/chem.201100200

文献信息

• Asymmetric Organocatalytic Direct Aldol Reactions of Ketones with α-Keto Acids and Their Application to the Synthesis of 2-Hydroxy-γ-butyrolactones
  作者：Xiao-Ying Xu、Zhuo Tang、Yan-Zhao Wang、Shi-Wei Luo、Lin-Feng Cun、Liu-Zhu Gong

  DOI：10.1021/jo701868t

  日期：2007.12.1

  of organocatalysts for the asymmetric direct aldol reactions of ketones with α-keto acids were designed on the basis of molecular recognition and prepared from proline and aminopyridines. The organic molecule 8e, derived from proline and 6-methyl-2-amino pyridine, was the best catalyst, affording excellent enantioselectivities (up to 98% ee) for the direct aldol reactions of acetone or 2-butanone with

  在分子识别的基础上，设计了多种有机催化剂，用于酮与α-酮酸的不对称直接羟醛直接反应，并由脯氨酸和氨基吡啶制备。有机分子8e衍生自脯氨酸和6-甲基-2-氨基吡啶的最佳催化剂，对丙酮或2-丁酮与各种α-酮酸和用于各种无环脂族酮与3-（2-硝基苯基）-2-氧代丙酸的反应。通过非对映选择性还原和内酯化的反应序列可以将羟醛加成物转化为2-羟基-γ-丁内酯。对过渡态的实验和理论研究表明，有机催化剂的酰胺N和吡啶N分别与α-酮酸的酮氧基和羧酸羟基选择性地形成氢键。这两个氢键相互作用对于直接不对称羟醛缩合的反应性和对映选择性很重要。
• Asymmetric Direct Aldol Reaction of Functionalized Ketones Catalyzed by Amine Organocatalysts Based on Bispidine
  作者：Jie Liu、Zhigang Yang、Zhen Wang、Fei Wang、Xiaohong Chen、Xiaohua Liu、Xiaoming Feng、Zhishan Su、Changwei Hu

  DOI：10.1021/ja800839w

  日期：2008.4.1

  Organocatalysts containing primary-secondary amine based on bispidine and amino acid have been designed to catalyze the asymmetric direct aldol reaction of functionalized ketones including alpha-keto phosphonates, alpha-keto esters, as well as alpha,alpha-dialkoxy ketones as aldol reaction acceptors. The corresponding products with chiral tertiary alcohols were obtained in moderate to high yields (up

  含有基于双吡啶和氨基酸的伯仲胺的有机催化剂已被设计用于催化功能化酮的不对称直接醛醇反应，包括 α-酮膦酸酯、α-酮酯以及作为醛醇反应受体的 α,α-二烷氧基酮。以中等至高产率（高达 97%）和高对映选择性（高达 98% ee）获得具有手性叔醇的相应产物。过渡结构的理论研究表明，质子化哌啶对该反应的反应性和对映选择性很重要。
• Synthesis of N,N′-Dialkylated Cyclohexane-1,2-diamines and Their Application as Asymmetric Ligands and Organocatalysts for the Synthesis of Alcohols
  作者：Denis Chusov、Alexey Tsygankov、Man-Seog Chun、Alexandra Samoylova、Seongyeon Kwon、Yuliya Kreschenova、Suhyeon Kim、Euijin Shin、Jinho Oh、Tatyana Strelkova、Valerii Kolesov、Fedor Zubkov、Sergei Semenov、Ivan Fedyanin

  DOI：10.1055/s-0036-1588382

  日期：——

  A series of N,N′-dialkylated derivatives of (1R,2R)-cyclohexane-1,2-diamine were synthesized, and a new approach to the one-pot preparation of this type of amine was demonstrated. The prepared diamines were used as organocatalysts for the two-step synthesis of α-hydroxy γ-keto esters from arenes, chlorooxoacetates, and ketones; they were also used as chiral ligands for Meervein–Ponndorf–Verley reductions

  合成了一系列(1R,2R)-环己烷-1,2-二胺的N,N'-二烷基化衍生物，并展示了该类胺的一锅法制备新方法。制备的二胺用作有机催化剂，用于从芳烃、氯代乙酸酯和酮两步合成α-羟基γ-酮酯；它们也被用作 Meervein-Ponndorf-Verley 还原和亨利反应的手性配体。
• Direct asymmetric aldol reaction of acetone with α-ketoesters catalyzed by primary–tertiary diamine organocatalysts
  作者：Zhaoqin Jiang、Yixin Lu

  DOI：10.1016/j.tetlet.2010.02.044

  日期：2010.4

  Novel primary–tertiary diamine organocatalysts derived from l-serine were utilized to promote enantioselective aldol reaction of acetone with α-ketoesters. The desired products were obtained in high yields and with good to excellent enantioselectivities (up to 95% ee).

  衍生自1-丝氨酸的新型伯-叔二胺有机催化剂被用于促进丙酮与α-酮酸酯的对映选择性醛醇缩合反应。以高收率和良好至优异的对映选择性（高达95％ee）获得所需产物。
• Stereospecific diaza-Cope rearrangement as an efficient tool for the synthesis of DPEDA pyridine analogs and related C₂-symmetric organocatalysts
  作者：A. S. Kucherenko、A. A. Kostenko、V. V. Gerasimchuk、S. G. Zlotin

  DOI：10.1039/c7ob01852e

  日期：——

  A simple and efficient synthesis of enantiomerically pure (1S,2S)-1,2-di(pyridin-2-yl)- and (1R,2R)-1,2-di(pyridin-4-yl)-ethane-1,2-diamines from commercial picolinaldehyde or isonicotinaldehyde and 2,2′-((1S,2S)-1,2-diaminoethane-1,2-diyl)diphenol (HPEN) via a stereospecific diaza-Cope rearrangement has been developed. Diamine (R,R)-2b was readily converted to novel diastereomeric ionic group-supported

  对映体纯的（1 S，2 S）-1,2-二（吡啶-2-基）-和（1 R，2 R）-1,2-二（吡啶-4-基）的简单有效的合成-乙烷-1,2-二胺从商业吡啶甲醛或异烟醛和2,2' - （（1-小号，2小号）-1,2-二氨基乙烷-1,2-二基）联苯酚（HPEN）通过立体有择二氮杂-应对重排已开发。二胺（R，R）-2b易于转化为新型非对映体离子基团支持的双脯氨酰胺（R，S）-1b和（R，R）-图1b似乎是在纯净条件下在醛/醛，酮/酮或酮/醛试剂体系中不对称交叉醛醇缩合反应的有效有机催化剂，以高收率和高达99％的ee提供相应的醛醇缩合。此外，催化剂（R，S）-1b可在相同或相似的催化反应中重复使用超过15次，表现出接近原始的活性和高水平的立体诱导。