benzyl (E)-β-acetylamino butenoate | 505092-90-0

• 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: benzyl (E)-β-acetylamino butenoate
• 英文别名: benzyl (E)-3-acetamido-2-butenoate；2-Butenoic acid, 3-(acetylamino)-, phenylmethyl ester, (2E)-；benzyl (E)-3-acetamidobut-2-enoate
• CAS: 505092-90-0
• 化学式: C₁₃H₁₅NO₃
• 分子量: 233.267
• InChiKey: NYVAYJMGDWOMQI-CSKARUKUSA-N

物化性质

• 熔点：
  104-106 °C
• 沸点：
  414.4±37.0 °C(Predicted)
• 密度：
  1.123±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  55.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  benzyl (E)-β-acetylamino butenoate 在 [Rh(COD)(R,R)-bis(diphenylphosphino)-1,3-(Ph₂)propane]BF₄ 、 氢气 作用下， 以 二氯甲烷 为溶剂， 25.0 ℃ 、101.32 kPa 条件下， 生成 (3S)-3-乙酰氨基丁酸苄酯
  参考文献：
  名称：

  Economic preparation of 1,3-diphenyl-1,3-bis(diphenylphosphino)propane: a versatile chiral diphosphine ligand for enantioselective hydrogenations

  摘要：

  The enantioselective hydrogenation of 1,3-diarylpropane-1,3-diones with chiral Ru(II)-diphosphine catalyst has been studied. In a first approach it was found, that Tol-BINAP together with Ru(COD)methallyl(2) formed the most selective catalyst. One of the C-2-symmetric enantiopure 1,3-diols obtained in turn was transformed via its 1,3-di-O-mesylate into 1,3-bisdiarylphosphines. One of them, 1,3-diphenyl-1,3-bis(diphenylphosphino)propane, could be advantageously utilized as a ligand for the efficient enantioselective Ru-catalyzed hydrogenation of its own 1,3-diketone precursor. Thus, the condition for a 'cross self-breeding' catalytic system is fulfilled. A further reduction of the preparation costs could be achived by application of RuCl3.H2O instead of other more expensive precatalyst precursors without compromosing the enantioselectivity. The ligand was used in the Rh(I)-catalyzed asymmetric hydrogenation of model substrates and beta-amino acid precursors where up to 97% ee could be achieved. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(03)00595-0
• 作为产物：
  描述：

  乙酰丙酮苄酯 、 alkaline earth salt of/the/ methylsulfuric acid 在 吡啶 、 ammonium acetate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 72.0h， 生成 benzyl (E)-β-acetylamino butenoate
  参考文献：
  名称：

  新型手性双膦烷配体的合成，用于Rh（I）催化异构体β-酰基酰胺基丙烯酸酯的对映选择性氢化。

  摘要：

  已经描述了手性甲硅烷基膦酸酯的高度立体选择性的合成，其可以在无碱条件下有利地用作构建与DuPHOS有关的二膦的结构单元。在合成新的双膦环烷配体1（MalPHOS）中显示了甲硅烷基膦环烷的效用，该双膦环烷配体1的特征是马来酸酐骨架。配体与Rh（I）形成比类似Me-DuPHOS复合物具有更大咬合角P-Rh-P的复合物。两种配合物均已在具有药物相关性的不饱和α-和β-氨基酸前体的不对称氢化中进行了测试。在某些情况下，与Me-DuPHOS配合物相比，这种新型催化剂更具优势，特别是当使用（Z）构型的β-酰氨基丙烯酸酯作为底物时。

  DOI：

  10.1021/jo020453h

文献信息

• A Highly Tunable Family of Chiral Bisphospholanes for Rh-Catalyzed Enantioselective Hydrogenation Reactions
  作者：Jens Holz、Odalys Zayas、Haijun Jiao、Wolfgang Baumann、Anke Spannenberg、Axel Monsees、Thomas H. Riermeier、Juan Almena、Renat Kadyrov、Armin Börner

  DOI：10.1002/chem.200600033

  日期：2006.6.23

  enantioselectivities in methanol as the solvent. This may account for optimised steric and electronic effects. However, by changing the solvent catalysts with other backbones can give rise to excellent results. This gives proof that simple correlations between steric and electronic properties and results in the enantioselective hydrogenation frequently claimed in literature are not general.

  通过使用高度灵活和收敛的方法，已经制备了一组16种新的且密切相关的双膦环烷配体。每种合成可以在工业上相关的规模上进行。双膦在连接两个膦酸酯单元的桥的性质上不同。桥由三元，四元，五元和六元杂环或脂环族环形成。通过使用理论计算（DFT）和分析测量结果（（31）P和（103）Rh NMR光谱，X射线结构分析）研究了双膦酮及其Rh预催化剂。研究表明，基于具有马来酸酐或马来酰亚胺桥的配体的催化剂在甲醇作为溶剂中具有不断优异的对映选择性。这可以说明优化的空间和电子效果。然而，通过改变溶剂催化剂与其他主链可以产生优异的结果。这证明了在空间性质和电子性质之间的简单关联以及导致文献中经常要求的对映选择性氢化的结果并不普遍。
• Economic preparation of 1,3-diphenyl-1,3-bis(diphenylphosphino)propane: a versatile chiral diphosphine ligand for enantioselective hydrogenations
  作者：Natalia V. Dubrovina、Vitali I. Tararov、Axel Monsees、Renat Kadyrov、Christine Fischer、Armin Börner

  DOI：10.1016/s0957-4166(03)00595-0

  日期：2003.9

  The enantioselective hydrogenation of 1,3-diarylpropane-1,3-diones with chiral Ru(II)-diphosphine catalyst has been studied. In a first approach it was found, that Tol-BINAP together with Ru(COD)methallyl(2) formed the most selective catalyst. One of the C-2-symmetric enantiopure 1,3-diols obtained in turn was transformed via its 1,3-di-O-mesylate into 1,3-bisdiarylphosphines. One of them, 1,3-diphenyl-1,3-bis(diphenylphosphino)propane, could be advantageously utilized as a ligand for the efficient enantioselective Ru-catalyzed hydrogenation of its own 1,3-diketone precursor. Thus, the condition for a 'cross self-breeding' catalytic system is fulfilled. A further reduction of the preparation costs could be achived by application of RuCl3.H2O instead of other more expensive precatalyst precursors without compromosing the enantioselectivity. The ligand was used in the Rh(I)-catalyzed asymmetric hydrogenation of model substrates and beta-amino acid precursors where up to 97% ee could be achieved. (C) 2003 Elsevier Ltd. All rights reserved.
• WO2006/45388
  申请人：——

  公开号：——

  公开（公告）日：——
• Synthesis of a New Chiral Bisphospholane Ligand for the Rh(I)-Catalyzed Enantioselective Hydrogenation of Isomeric β-Acylamido Acrylates
  作者：Jens Holz、Axel Monsees、Haijun Jiao、Jinsong You、Igor V. Komarov、Christine Fischer、Karlheinz Drauz、Armin Börner

  DOI：10.1021/jo020453h

  日期：2003.3.1

  The highly stereoselective synthesis of a chiral silylphospholane has been described, which can be advantageously used as a building block under base-free conditions for the construction of diphosphines related to DuPHOS. The utility of silylphospholane is shown in the synthesis of a new bisphospholane ligand 1 (MalPHOS), which is characterized by a maleic anhydride backbone. The ligand forms with

  已经描述了手性甲硅烷基膦酸酯的高度立体选择性的合成，其可以在无碱条件下有利地用作构建与DuPHOS有关的二膦的结构单元。在合成新的双膦环烷配体1（MalPHOS）中显示了甲硅烷基膦环烷的效用，该双膦环烷配体1的特征是马来酸酐骨架。配体与Rh（I）形成比类似Me-DuPHOS复合物具有更大咬合角P-Rh-P的复合物。两种配合物均已在具有药物相关性的不饱和α-和β-氨基酸前体的不对称氢化中进行了测试。在某些情况下，与Me-DuPHOS配合物相比，这种新型催化剂更具优势，特别是当使用（Z）构型的β-酰氨基丙烯酸酯作为底物时。
• New chiral 1,3-diphosphine ligands for Rh-catalyzed enantioselective hydrogenation: a search for electronic effects
  作者：Natalia V. Dubrovina、Vitali I. Tararov、Axel Monsees、Anke Spannenberg、Ioannis D. Kostas、Armin Börner

  DOI：10.1016/j.tetasy.2005.08.048

  日期：2005.11

  New electron-rich chiral 1,3-diphosphines of the BDPP type were prepared from 1, 3-diphenylpropane- 1,3-diol by an economically feasible synthetic approach. The a-donor properties of the phosphines were determined by measurement of J(P-31-Se-77) coupling constants in the corresponding phosphine selenides. For comparison related, but electronically different, 1,3-diphosphines were considered. The new diphosphines showed good enantioselectivities as ligands in the Rh-catalyzed enantioselective hydrogenation of benchmark substrates and beta-amino acid precursors (up to 98% ee). The electronic effects on the outcome of the enantioselective catalysis have been analyzed. (c) 2005 Published by Elsevier Ltd.