O-(2-methacryloyloxyethylsuccinoyl)-trans-4-hydroxy-α,α-di-phenyl-L-prolinol hydrochloride | 1173035-69-2

• 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: O-(2-methacryloyloxyethylsuccinoyl)-trans-4-hydroxy-α,α-di-phenyl-L-prolinol hydrochloride
• 英文别名: O-(2-methacryloyloxyethylsuccinoyl)-trans-4-hydroxy-α,α-diphenyl-L-prolinol hydrochloride；4-O-[(3R,5S)-5-[hydroxy(diphenyl)methyl]pyrrolidin-3-yl] 1-O-[2-(2-methylprop-2-enoyloxy)ethyl] butanedioate;hydrochloride
• CAS: 1173035-69-2
• 化学式: C₂₇H₃₁NO₇*ClH
• 分子量: 518.007
• InChiKey: DHRVPGSHYOMNRK-RFPXDPOKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.06
• 重原子数：
  36
• 可旋转键数：
  14
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  111
• 氢给体数：
  3
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  O-(2-methacryloyloxyethylsuccinoyl)-trans-4-hydroxy-α,α-di-phenyl-L-prolinol hydrochloride 在 potassium carbonate 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 0.08h， 以100%的产率得到O-(2-methacryloyloxyethylsuccinoyl)-trans-4-hydroxy-α,α-di-phenyl-L-prolinol
  参考文献：
  名称：

  Enantioselectivity, swelling and stability of 4-hydroxyprolinol containing acrylic polymer beads in the asymmetric reduction of ketones

  摘要：

  A new 4-hydroxy-alpha,alpha-diphenyl-L-prolinol containing polymethacrylate, prepared without chromatography by a large scale adaptable synthesis, has been evaluated as a catalyst in the asymmetric reduction of 1-arylethanones. Using 1-(4-bromophenyl)ethanone as the model substance, the reduction was tested with various borane sources and solvents. The best swellings of the polymer and reactivity were observed in THF using N,N-diethylaniline borane complex as the hydride source. The selectivity in the reduction of 1-(4-bromophenyl)ethanone was found to depend on the substrate concentration and catalyst loading. Using the best conditions identified, a series of 1-arylethanones was reduced to their corresponding enantioenriched secondary alcohols. High rates and ee-values were obtained in the reduction of acetophenones containing electron withdrawing groups in the aromatic ring, whereas a moderate selectivity was the result for products containing electron donating aromatic substituents. Upon recovery of the polymer beads, it was found that vacuum drying led to extensive rupturing, while the bead structure was intact if washed with methanol and air dried at atmospheric pressure. Repeated use of the polymer catalyst gave the product alcohol with a lower 90% ee. Elemental analysis showed this to be due to the loss of the chiral prolinol unit. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2011.12.001
• 作为产物：
  描述：

  (4R)-4-羟基-L-脯氨酸盐酸盐 在 magnesium 、 三氟乙酸 作用下， 以 乙醚 为溶剂， 反应 2.0h， 生成 O-(2-methacryloyloxyethylsuccinoyl)-trans-4-hydroxy-α,α-di-phenyl-L-prolinol hydrochloride
  参考文献：
  名称：

  A heterogeneous layered bifunctional catalyst for the integration of aerobic oxidation and asymmetric C–C bond formation

  摘要：

  报道了用于一级烯丙醇与二苄基丙二酸酯顺序氧气氧化-不对称迈克尔反应的非均相双功能手性催化剂的设计与合成。有趣的是，我们发现将双金属纳米粒子层叠在手性复合材料中的有机催化剂上，对催化活性至关重要。

  DOI：

  10.1039/c3cc46204h

文献信息

• A General Approach for Preparation of Polymer-Supported Chiral Organocatalysts via Acrylic Copolymerization
  作者：Tor E. Kristensen、Kristian Vestli、Martin G. Jakobsen、Finn K. Hansen、Tore Hansen

  DOI：10.1021/jo902585j

  日期：2010.3.5

  Polymer-supported chiral organocatalysts, as well as most other forms of immobilized catalysts! arc traditionally prepared by a postmodification approach where modified catalyst precursors are anchored onto prefabricated polymer beads. Herein, we report an alternative and more scalable approach where polymer-supported chiral enamine and iminium organocatalysts are prepared in a bottom-up fashion where methacrylic functional monomers are prepared in an entirely nonchromatographic manner and subsequently copolymerized with suitable comonomers to give cross-linked polymer beads. All syntheses have been conducted on multigram scale for all intermediates and finished polymer products, and the catalysts have proven successful in reactions taking place in solvents spanning a wide range of solvent polarity. While polymer-supported proline and proline-amides generally demonstrated excellent results and recycling robustness in asymmetric aldol reactions or ketones and benzaldehydes, the simplest type of Jorgensen/Hayashi diarylprolinol TMS-ether showed excellent selectivity, but rather sluggish reactivity in the Enders-type asymmetric cascade. The polymer-supported version of the first-generation MacMillan imidazolidinone had a pattern of reactivity very similar to that of the monomeric catalyst, but is too unstable to allow recycling.
• Enantioselectivity, swelling and stability of 4-hydroxyprolinol containing acrylic polymer beads in the asymmetric reduction of ketones
  作者：Thor H. Krane Thvedt、Tor Erik Kristensen、Eirik Sundby、Tore Hansen、Bård Helge Hoff

  DOI：10.1016/j.tetasy.2011.12.001

  日期：2011.12

  A new 4-hydroxy-alpha,alpha-diphenyl-L-prolinol containing polymethacrylate, prepared without chromatography by a large scale adaptable synthesis, has been evaluated as a catalyst in the asymmetric reduction of 1-arylethanones. Using 1-(4-bromophenyl)ethanone as the model substance, the reduction was tested with various borane sources and solvents. The best swellings of the polymer and reactivity were observed in THF using N,N-diethylaniline borane complex as the hydride source. The selectivity in the reduction of 1-(4-bromophenyl)ethanone was found to depend on the substrate concentration and catalyst loading. Using the best conditions identified, a series of 1-arylethanones was reduced to their corresponding enantioenriched secondary alcohols. High rates and ee-values were obtained in the reduction of acetophenones containing electron withdrawing groups in the aromatic ring, whereas a moderate selectivity was the result for products containing electron donating aromatic substituents. Upon recovery of the polymer beads, it was found that vacuum drying led to extensive rupturing, while the bead structure was intact if washed with methanol and air dried at atmospheric pressure. Repeated use of the polymer catalyst gave the product alcohol with a lower 90% ee. Elemental analysis showed this to be due to the loss of the chiral prolinol unit. (C) 2011 Elsevier Ltd. All rights reserved.
• A heterogeneous layered bifunctional catalyst for the integration of aerobic oxidation and asymmetric C–C bond formation
  作者：Hiroyuki Miyamura、Gerald C. Y. Choo、Tomohiro Yasukawa、Woo-Jin Yoo、Shu Kobayashi

  DOI：10.1039/c3cc46204h

  日期：——

  The design and synthesis of a heterogeneous bifunctional chiral catalyst for the sequential aerobic oxidation–asymmetric Michael reactions between primary allylic alcohols and dibenzyl malonate are described. Interestingly, we found that layering bimetallic nanoparticles over the organocatalyst, within the chiral composite material, is crucial for catalytic activity.

  报道了用于一级烯丙醇与二苄基丙二酸酯顺序氧气氧化-不对称迈克尔反应的非均相双功能手性催化剂的设计与合成。有趣的是，我们发现将双金属纳米粒子层叠在手性复合材料中的有机催化剂上，对催化活性至关重要。