2-oxo-propionic acid benzhydryl ester | 848598-59-4

• 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: 2-oxo-propionic acid benzhydryl ester
• 英文别名: diphenylmethyl pyruvate；benzhydryl 2-oxopropanoate；Propanoic acid, 2-oxo-, diphenylmethyl ester
• CAS: 848598-59-4
• 化学式: C₁₆H₁₄O₃
• 分子量: 254.285
• InChiKey: PTONPIMWLSQVBS-UHFFFAOYSA-N

物化性质

• 沸点：
  387.9±31.0 °C(Predicted)
• 密度：
  1.157±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-苯基-1-三甲基硅氧乙烯 、 2-oxo-propionic acid benzhydryl ester 在 lutetium triflate (4S,5S)-2,6-bis[5-Ph-4-(iPrO)3-OSi-Me-1,3-oxazolin-2-yl]Py 作用下， 以 二氯甲烷 为溶剂， 反应 96.0h， 以95%的产率得到(+)-(S)-diphenylmethyl 2-hydroxy-2-methyl-4-oxo-4-phenylbutanoate
  参考文献：
  名称：

  镧系元素/Pybox配合物催化丙酮酸和1-苯基-1-三甲基甲硅烷氧基乙烯的对映选择性Mukaiyama-Aldol反应

  摘要：

  1-苯基-1-三甲基甲硅烷氧基乙烯 (1) 和三种丙酮酸 (2a-c) 之间的对映选择性 Mukaiyama-醛醇反应由 (4S,5S)-2,6-双 [5-苯基-4 的镧系元素三氟甲磺酸盐络合物催化-(三异丙基甲硅烷氧基)甲基-1,3-恶唑啉-2-基]吡啶(3)。最好的催化剂是基于 LuIII 和 ScIII 的配合物，它们可以提供高产率 (S)-4a-c 和高达 99.5% 的对映体过量。基于 LaIII 的配合物有利于形成相反的对映异构体 [(R)-4c 的 77% ee]。提出了立体化学结果的基本原理。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

  DOI：

  10.1002/ejoc.200600716
• 作为产物：
  描述：

  丙酮酸乙酯 、 二苯甲醇 在 iron(III)-acetylacetonate 、 sodium carbonate 作用下， 以 正庚烷 为溶剂， 反应 6.0h， 以95%的产率得到2-oxo-propionic acid benzhydryl ester
  参考文献：
  名称：

  Transesterification catalyzed by iron(III) β-diketonate species

  摘要：

  A practical and clean protocol for transesterification catalyzed by a 5 mol % cheap, non-toxic and moisture stable Fe(acac)(3) or other iron(III) beta-diketonate species in solvent, such as heptane under azeotropic condition is developed. A remarkable rate enhancement was observed upon the addition of 5 mol % of an inorganic base, such as Na2CO3, which suggests that faster formation of a dimeric mu-alkoxy-bridged iron (III) species under alkaline conditions facilitates catalytic turnover. This system provides smooth transesterification over a wide range of structurally diverse esters and alcohols without disturbing functional groups. In addition, the use of iron beta-diketonate complexes as catalysts is more environmentally friendly, safer, and economical than other transition-metal catalysts. Preliminary mechanistic studies indicate that the active catalyst is likely a dimeric mu-alkoxy-bridged iron(III) species, as determined by X-ray crystallography of [Fe(dbm)(2)(O-n-Bu)](2) derived from the alcoholysis of Fe(dbm)(3) under alkaline conditions. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.01.009

文献信息

• Nucleophilic β-Carbon Activation of Propionic Acid as a 3-Carbon Synthon by Carbene Organocatalysis
  作者：Zhichao Jin、Ke Jiang、Zhenqian Fu、Jaume Torres、Pengcheng Zheng、Song Yang、Bao-An Song、Yonggui Robin Chi

  DOI：10.1002/chem.201501481

  日期：2015.6.22

  Direct β‐carbon activation of propionic acid (C2H5CO2H) by carbene organocatalysis has been developed. This activation affords the smallest azolium homoenolate intermediate (without any substituent) as a 3‐carbon nucleophile for enantioselective reactions. Propionic acid is an excellent raw material because it is cheap, stable, and safe. This approach provides a much better solution to azolium homoenolate

  已经开发了通过卡宾有机催化作用对丙酸（C 2 H 5 CO 2 H）进行直接β-碳活化。这种活化提供了最小的均氮唑鎓中间体（无任何取代基），作为对映选择性反应的3碳亲核试剂。丙酸是便宜，稳定和安全的原料，因此是一种极好的原料。这种方法比以前建立的丙烯醛（没有任何取代基的烯醛）使用昂贵，不稳定且有毒的方法提供了更好的解决方案，用于合成均氮唑鎓。
• Catalytic Enantioselective Synthesis of <i>N</i> , <i>N</i> ‐Acetals from α‐Dicarbonyl Compounds Using Chiral Imidazoline‐Phosphoric Acid Catalysts
  作者：Shuichi Nakamura、Tatsumi Wada、Tsunayoshi Takehara、Takeyuki Suzuki

  DOI：10.1002/adsc.202001128

  日期：2020.12.8

  The enantioselective synthesis of chiral N,N‐acetals derived from α‐dicarbonyl compounds has been achieved. Good yields and enantioselectivities were observed for the reaction with various α‐dicarbonyl compounds with 2‐aminobenzamides using chiral bis(imidazoline)‐phosphoric acid catalysts. Based on these experimental investigations, a possible transition state is proposed to explain the origin of

  已经实现了从α-二羰基化合物衍生的手性N，N-缩醛的对映选择性合成。使用手性双（咪唑啉）-磷酸催化剂与各种α-二羰基化合物与2-氨基苯甲酰胺的反应观察到良好的收率和对映选择性。基于这些实验研究，提出了一种可能的过渡态来解释不对称感应的起源。
• Nucleophilic Acyl Substitutions of Anhydrides with Protic Nucleophiles Catalyzed by Amphoteric, Oxomolybdenum Species
  作者：Chien-Tien Chen、Jen-Huang Kuo、Vijay D. Pawar、Yogesh S. Munot、Shieu-Shien Weng、Cheng-Hsiu Ku、Cheng-Yuan Liu

  DOI：10.1021/jo048363v

  日期：2005.2.1

  [GRAPHICS]Among six different group VIb oxometallic species examined, dioxomolybdenum dichloride and oxomolybdenum tetrachloride were the most efficient catalysts to facilitate nucleophilic acyl substitution (NAS) of anhydrides with a myriad array of alcohols, amines, and thiols in high yields and high chemoselectivity. In contrast to the well-recognized redox chemical behaviors associated with oxomolybdenum(VI) species, the catalytic NAS was unprecedented and tolerates virtually all kinds of functional groups. By using benzoic anhydride as a mediator for in situ generation of an incipient mixed anhydride -MoO2Cl2 adduct with a given functional alkanoic acid, one can achieve oleate, dipeptide, diphenylmethyl, N-Fmoc-alpha-amino, pyruvic, and tert-butylthio ester, N-tert-butylamide, and trityl methacrylate syntheses with appropriate protic nucleophiles. The amphoteric character of the Mo=O unit in oxomolybdenum chlorides was found to be responsible for the catalytic NAS profile as supported by a control NAS reaction of using an authentic adduct-MoOCl2(O-2-CBut)(2) between pivalic anhydride and MoO2Cl2 as the catalyst.
• Transesterification catalyzed by iron(III) β-diketonate species
  作者：Shiue-Shien Weng、Chih-Shueh Ke、Fong-Kuang Chen、You-Fu Lyu、Guan-Ying Lin

  DOI：10.1016/j.tet.2011.01.009

  日期：2011.3

  A practical and clean protocol for transesterification catalyzed by a 5 mol % cheap, non-toxic and moisture stable Fe(acac)(3) or other iron(III) beta-diketonate species in solvent, such as heptane under azeotropic condition is developed. A remarkable rate enhancement was observed upon the addition of 5 mol % of an inorganic base, such as Na2CO3, which suggests that faster formation of a dimeric mu-alkoxy-bridged iron (III) species under alkaline conditions facilitates catalytic turnover. This system provides smooth transesterification over a wide range of structurally diverse esters and alcohols without disturbing functional groups. In addition, the use of iron beta-diketonate complexes as catalysts is more environmentally friendly, safer, and economical than other transition-metal catalysts. Preliminary mechanistic studies indicate that the active catalyst is likely a dimeric mu-alkoxy-bridged iron(III) species, as determined by X-ray crystallography of [Fe(dbm)(2)(O-n-Bu)](2) derived from the alcoholysis of Fe(dbm)(3) under alkaline conditions. (C) 2011 Elsevier Ltd. All rights reserved.
• Enantioselective Mukaiyama-Aldol Reaction of Pyruvates and 1-Phenyl- 1-trimethylsilyloxyethene Catalyzed by Lanthanide/Pybox Complexes
  作者：Giovanni Desimoni、Giuseppe Faita、Francesca Piccinini、Marco Toscanini

  DOI：10.1002/ejoc.200600716

  日期：2006.12

  1-phenyl-1-trimethylsilyloxyethene (1) and three pyruvates (2a–c) is catalyzed by the lanthanide triflate complexes of(4S,5S)-2,6-bis[5-phenyl-4-(triisopropylsilyloxy)methyl-1,3-oxazolin-2-yl]pyridine (3). The best catalysts are the LuIII- and ScIII-based complexes that give high yields of (S)-4a–c and enantiomeric excesses up to 99.5 %. The LaIII-based complex favors the formation of the opposite enantiomer

  1-苯基-1-三甲基甲硅烷氧基乙烯 (1) 和三种丙酮酸 (2a-c) 之间的对映选择性 Mukaiyama-醛醇反应由 (4S,5S)-2,6-双 [5-苯基-4 的镧系元素三氟甲磺酸盐络合物催化-(三异丙基甲硅烷氧基)甲基-1,3-恶唑啉-2-基]吡啶(3)。最好的催化剂是基于 LuIII 和 ScIII 的配合物，它们可以提供高产率 (S)-4a-c 和高达 99.5% 的对映体过量。基于 LaIII 的配合物有利于形成相反的对映异构体 [(R)-4c 的 77% ee]。提出了立体化学结果的基本原理。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)