dl-Aethyl 2-benzyl-3-oxo-5-phenylpentanoat | 67373-58-4

• 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: dl-Aethyl 2-benzyl-3-oxo-5-phenylpentanoat
• 英文别名: Ethyl 2-benzyl-3-oxo-5-phenylpentanoate
• CAS: 67373-58-4
• 化学式: C₂₀H₂₂O₃
• 分子量: 310.393
• InChiKey: YTIKJXZUZSOSTG-UHFFFAOYSA-N

物化性质

• 沸点：
  426.8±30.0 °C(Predicted)
• 密度：
  1.096±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  23
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.3
• 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：

  dl-Aethyl 2-benzyl-3-oxo-5-phenylpentanoat 在 potassium 1-hydroxy-1,3-dioxo-1,3-dihydro-1λ(5)-benziodoxol-5-sulfonate 、 甲基三辛基氯化铵 、 sodium chloride 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 24.0h， 以82%的产率得到ethyl 2-benzyl-2-chloro-3-oxo-5-phenylpentanoate
  参考文献：
  名称：

  氯化钠对活化亚甲基化合物的氧化氯化

  摘要：

  描述了一种用于直接氯化 1,3-二羰基化合物（和相关化合物，如 α-氰基酮）的操作简单的协议。该过程依赖于使用 IBX-SO 3 K 作为化学计量氧化剂和无处不在的氯化钠的温和条件。相转移催化剂的存在有助于在 THF-水混合物中获得良好的产率。

  DOI：

  10.1055/s-0033-1340793
• 作为产物：
  描述：

  3-苯丙酸乙酯 在 正丁基锂 、 (3-hydroxy)butyl p-tolyl sulfone 作用下， 以 四氢呋喃 为溶剂， 以78%的产率得到dl-Aethyl 2-benzyl-3-oxo-5-phenylpentanoat
  参考文献：
  名称：

  Facile Intramolecular Acylation Reactions of .gamma.- and .delta.-(Acyloxy)Sulfones: Synthesis of Substituted Chiral Dihydrofurans and Dihydropyrans

  摘要：

  The acylation ai (S)-4-(p-tolylsulfonly)-2-butanol and (S)-(p-tolylsulfonyl)-3-pentanal, chirons that are available in high optical purities, with a variety of acid chlorides gave the corresponding derivatives 9-16. Deprotonation of these substrates with LHMDS in THF at -78 degrees C led to the selective formation of the or-sulfonyl carbanions. These carbanions cyclized readily to give in good yields an equilibrium mixture of the expected lactols with the open chain hydroxy ketones. This ring closure/acyl transfer reaction was facile and found to be compatible with functionalities such as halides and esters in the acyl side chain. The mixture of lactols with the open chain hydroxy ketones obtained from this reaction could be dehydrated in good yields using mild acid conditions to give the corresponding chiral nonracemic dihydrofurans or dihydropyrans. Alternatively, this equilibrium mixture could be trapped as the open-chain (tert-butyldimethylsilyl) oxy ketosulfone derivatives 32-35 and subsequently desulfonylated.

  DOI：

  10.1021/jo00087a014

文献信息

• Synthesis of optically active .ALPHA.-alkyl or .ALPHA.-aryl acids from L-.ALPHA.-amino acids by the use of organocopper reagents.
  作者：SHIRO TERASHIMA、CHUNGCHYI TSENG、KENJI KOGA

  DOI：10.1248/cpb.27.747

  日期：——

  With an aim to further explore the utility of L-α-amino acids (I) in the synthesis of optically active compounds, the reaction of optically active α-tosyloxy acids and their derivatives (III) readily obtainable from I, with several types of organocopper reagents were studied. Although there still remain some ambiguity in the formation of unusual reaction products such as the β-keto ester (dl-6) and the vicinal diol ((R)(+)-13) and in lower yields for the substitution products, it has become evident that when optically active α-tosyloxy acids prepared from L-phenylalanine, L-alanine, and L-leucine, respectively, are treated with lithium dialkyl- or diarylcuprates, the substitution reactions can proceed with almost full inversion to give corresponding optically active α-alkyl or α-aryl acids in max. 63% yield.

  为了进一步探索L-α-氨基酸(I)在光学活性化合物合成中的用途，由I容易获得光学活性α-甲苯磺酰氧基酸及其衍生物(III)与几种类型的反应研究了有机铜试剂。尽管在形成不寻常的反应产物（如 β-酮酯 (dl-6) 和邻二醇 ((R)(+)-13））以及取代产物的产率较低方面仍然存在一些模糊性，但它已经很明显，当分别由L-苯丙氨酸、L-丙氨酸和L-亮氨酸制备的光学活性α-甲苯磺酰氧基酸用二烷基铜或二芳基铜酸锂处理时，取代反应可以几乎完全反转进行，得到相应的光学活性最大 α-烷基或 α-芳基酸收率63%。
• Facile Intramolecular Acylation Reactions of .gamma.- and .delta.-(Acyloxy)Sulfones: Synthesis of Substituted Chiral Dihydrofurans and Dihydropyrans
  作者：Hollie K. Jacobs、Aravamudan S. Gopalan

  DOI：10.1021/jo00087a014

  日期：1994.4

  The acylation ai (S)-4-(p-tolylsulfonly)-2-butanol and (S)-(p-tolylsulfonyl)-3-pentanal, chirons that are available in high optical purities, with a variety of acid chlorides gave the corresponding derivatives 9-16. Deprotonation of these substrates with LHMDS in THF at -78 degrees C led to the selective formation of the or-sulfonyl carbanions. These carbanions cyclized readily to give in good yields an equilibrium mixture of the expected lactols with the open chain hydroxy ketones. This ring closure/acyl transfer reaction was facile and found to be compatible with functionalities such as halides and esters in the acyl side chain. The mixture of lactols with the open chain hydroxy ketones obtained from this reaction could be dehydrated in good yields using mild acid conditions to give the corresponding chiral nonracemic dihydrofurans or dihydropyrans. Alternatively, this equilibrium mixture could be trapped as the open-chain (tert-butyldimethylsilyl) oxy ketosulfone derivatives 32-35 and subsequently desulfonylated.
• Oxidative Chlorination of Activated Methylene Compounds with Sodium Chloride
  作者：Stefan Kirsch、Klaus-Daniel Umland、Camilla Mayer

  DOI：10.1055/s-0033-1340793

  日期：——

  An operationally simple protocol for the direct chlorination of 1,3-dicarbonyls (and related compounds such as α-cyano ­ketones) is described. The procedure relies on mild conditions using IBX–SO 3 K as the stoichiometric oxidizing agent and the ubiquitous sodium chloride. The presence of a phase-transfer catalyst is supportive to obtain good yields in a THF–water mixture.

  描述了一种用于直接氯化 1,3-二羰基化合物（和相关化合物，如 α-氰基酮）的操作简单的协议。该过程依赖于使用 IBX-SO 3 K 作为化学计量氧化剂和无处不在的氯化钠的温和条件。相转移催化剂的存在有助于在 THF-水混合物中获得良好的产率。