(S)-1-phenylethyl 3-phenylpropanoate | 52126-27-9

• 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: (S)-1-phenylethyl 3-phenylpropanoate
• 英文别名: [(1S)-1-phenylethyl] 3-phenylpropanoate
• CAS: 52126-27-9
• 化学式: C₁₇H₁₈O₂
• 分子量: 254.329
• InChiKey: WUDCDDNQDMUSIY-AWEZNQCLSA-N

物化性质

• 沸点：
  355.8±11.0 °C(Predicted)
• 密度：
  1.074±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  3-苯丙酰氯 在 吡啶 、 BES buffer 、 Lipase from Burkholderia cepacia 、 calcium chloride 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 48.0h， 生成 (S)-1-phenylethyl 3-phenylpropanoate
  参考文献：
  名称：

  How Substrate Solvation Contributes to the Enantioselectivity of Subtilisin toward Secondary Alcohols

  摘要：

  The current rule to predict the enantiopreference of subtilisin toward secondary alcohols is based on the size of the substituents at the stereocenter and implies that the active site contains two differently sized pockets for these substituents. Several experiments are inconsistent with the current rule. First, the X-ray structures of subtilisin show there is only one pocket (the S1' pocket) approximately the size of a phenyl group to bind secondary alcohols. Second, the rule often predicts the incorrect enantiomer for reactions in water. To resolve these contradictions, we refine the current rule to show that subtilisin binds only one substituent of a secondary alcohol and leaves the other in solvent. To test this refined empirical rule, we show that the enantioselectivity of a series of secondary alcohols in water varied linearly with the difference in hydrophobicity (log P/P0) of the substituents. This hydrophobicity difference accounts for the solvation of one substituent in water.

  DOI：

  10.1021/ja0528937

文献信息

• Protonation of Homoenolate Equivalents Generated by N-Heterocyclic Carbenes
  作者：Karl Scheidt、Brooks Maki、Audrey Chan

  DOI：10.1055/s-2008-1072516

  日期：2008.4

  Homoenolate equivalents are generated by Lewis basic N-heterocyclic carbene catalysts and then protonated to generate efficiently saturated esters from unsaturated aldehydes. This reactivity is extended to the generation of beta-acylvinyl anions from alkynyl aldehydes. The asymmetric protonation of a homoenolate equivalent generated from a beta,beta-disubstituted aldehyde can be accomplished with a

  Homoenolate 等价物由路易斯碱性 N-杂环卡宾催化剂生成，然后质子化以从不饱和醛有效生成饱和酯。这种反应性扩展到从炔醛生成 β-酰基乙烯基阴离子。由 β,β-二取代醛生成的同烯醇化物等价物的不对称质子化可以用手性 N-杂环卡宾完成。
• Conversion of α,β-Unsaturated Aldehydes into Saturated Esters: An Umpolung Reaction Catalyzed by Nucleophilic Carbenes
  作者：Audrey Chan、Karl A. Scheidt

  DOI：10.1021/ol050100f

  日期：2005.3.1

  species from alpha,beta-unsaturated aldehydes. These nucleophilic intermediates can be protonated, and the resulting activated carbonyl unit is trapped with an alcohol nucleophile, thereby promoting a highly efficient conversion of an alpha,beta-unsaturated aldehyde into a saturated ester. A kinetic resolution of secondary alcohols can be achieved using chiral imidazoylidene catalysts. [reaction: see text]

  衍生自苯并咪唑鎓盐的N-杂环卡宾是从α，β-不饱和醛生成均烯酸酯物种的有效催化剂。这些亲核中间体可以被质子化，并且所形成的活化羰基单元被醇亲核体捕获，从而促进α，β-不饱和醛向饱和酯的高效转化。仲醇的动力学拆分可以使用手性咪唑基亚烷基催化剂来实现。[反应：看文字]
• Catalytic, Enantioselective β-Protonation through a Cooperative Activation Strategy
  作者：Michael H. Wang、David Barsoum、C. Benjamin Schwamb、Daniel T. Cohen、Brian C. Goess、Matthias Riedrich、Audrey Chan、Brooks E. Maki、Rama K. Mishra、Karl A. Scheidt

  DOI：10.1021/acs.joc.7b00334

  日期：2017.5.5

  only feasible, but also adaptable to a kinetic resolution of secondary alcohols through NHC-catalyzed acylation. In-depth analysis of this process determined that careful catalyst and solvent pairing is critical for optimal yield and selectivity; proper choice of nonpolar solvent provided improved yield through suppression of an oxidative side reaction, while employment of a cooperative catalytic approach

  通过有机催化均烯酸酯方法对NHC催化的不饱和醛向饱和酯的转化已进行了深入研究。利用独特的“ Umpolung ”介导的β质子化，该过程已经从用于均烯酸酯反应性的测试台发展为用于不对称催化的更广泛的平台。受到我们成功使用β质子化过程从具有良好E / Z的艾纳尔中产生enals的启发选择性，我们的早期研究发现该反应的不对称变化不仅可行，而且还可以通过NHC催化的酰化反应适应仲醇的动力学拆分。对这一过程的深入分析表明，仔细的催化剂和溶剂配对对于获得最佳收率和选择性至关重要。非极性溶剂的适当选择提供通过氧化副反应的抑制提高的产量，而就业合作催化方法通过包含氢键供体助催化剂的显著提高对映选择性。
• The Specificity of the Nucleophilic Site of α-Chymotrypsin and its Potential for the Resolution of Alcohols. Enzyme-catalyzed Hydrolyses of Some (+)-, (−)-, and (±)-2-Butyl, -2-Octyl, and -α-Phenethyl Esters
  作者：Yong Yeng Lin、David N. Palmer、J. Bryan Jones

  DOI：10.1139/v74-075

  日期：1974.2.1

  The α-chymotrypsin-catalyzed hydrolyses of a representative spectrum of (R)- and (S)-2-butyl, -2-octyl, and -α-phenethyl esters of N-acetyl-L-phenylalanine, N-acetylglycine, α-hydroxy-β-phenyl-propionic, dihydrocinnamic, and hippuric acids have been examined. The kinetic studies were carried out in order to provide data on the practicability of exploiting the stereospecificity of the nucleophilic region

  N-乙酰基-L-苯丙氨酸、N-乙酰基甘氨酸、α-(R)-和(S)-2-丁基、-2-辛基和-α-苯乙酯的代表性光谱的α-胰凝乳蛋白酶催化水解-羟基-β-苯基-丙酸、二氢肉桂酸和马尿酸已经过检测。进行动力学研究是为了提供关于利用酶活性位点亲核区域的立体特异性通过选择性水解外消旋醇的酯来拆分外消旋醇的可行性的数据。获得的数据表明醇部分的结构和手性影响底物的催化和结合常数，并且对于二氢肉桂酸酯和马尿酸盐系列的非特异性底物观察到对映体醇部分之间的最大差异。
• 2,2-Disubstituted Propionic Anhydrides: Effective Coupling Reagents for the Kinetic Resolution of Secondary Benzylic Alcohols Using BTM
  作者：Isamu Shiina、Kenya Nakata、Masuhiro Sugimoto、Yu-suke Onda、Takashi Iizumi、Keisuke Ono

  DOI：10.3987/com-08-s(f)75

  日期：——

  variety of optically active benzylic alcohols possessing aliphatic substituents at the C-1 position are produced by the kinetic resolution of racemic secondary alcohols using free carboxylic acids with 2,2-disubstituted propionic anhydrides and (+)-benzotetramisole (BTM). Evaluation of the efficiency of this asymmetric esterification using several anhydrides derived from aliphatic carboxylic acids were carried

  通过使用游离羧酸与 2,2-二取代丙酸酐和 (+)-苯并四咪唑 (BTM) 进行外消旋仲醇的动力学拆分，可以生成各种在 C-1 位具有脂肪族取代基的光学活性苯甲醇。通过比较 (±)-1-苯基-1-丙醇的动力学拆分效率来评估使用衍生自脂肪族羧酸的几种酸酐的这种不对称酯化的效率。发现不仅新戊酸酐是在 BTM 存在下生产具有高 ee 的相应酯的非常广泛使用的试剂，而且其他 2,2-二取代丙酸酐，例如 2-甲基-2-苯基丙酸酐 (MPPRA ) 和 2,2-二苯丙酸酐 (DPPRA)，也可作为有效的偶联剂用于生产具有高选择性的旋光酯和醇。该协议通过利用转酰基化过程从酸组分和空间位阻羧酸酐中生成混合酸酐，直接从游离羧酸和外消旋仲醇中提供手性羧酸酯。