(2S,4R)-2-(diphenyl((trimethylsilyl)oxy)methyl)-4-(prop-2-yn-1-yloxy)pyrrolidine | 1218989-20-8

• 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: (2S,4R)-2-(diphenyl((trimethylsilyl)oxy)methyl)-4-(prop-2-yn-1-yloxy)pyrrolidine
• 英文别名: [diphenyl-[(2S,4R)-4-prop-2-ynoxypyrrolidin-2-yl]methoxy]-trimethylsilane
• CAS: 1218989-20-8
• 化学式: C₂₃H₂₉NO₂Si
• 分子量: 379.574
• InChiKey: FBHCBAVZCDZMCT-YADHBBJMSA-N

物化性质

• 沸点：
  474.5±45.0 °C(Predicted)
• 密度：
  1.07±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.16
• 重原子数：
  27
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  30.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2S,4R)-2-(diphenyl((trimethylsilyl)oxy)methyl)-4-(prop-2-yn-1-yloxy)pyrrolidine 、 叔丁基二甲硅基三氟甲磺酸酯 在 2,6-二甲基吡啶 作用下， 以 二氯甲烷 为溶剂， 以68%的产率得到(2S,4R)-2-(((tertbutyldimethylsilyl)oxy)diphenylmethyl)-4-(prop-2-yn-1-yloxy)pyrrolidine
  参考文献：
  名称：

  碳酸钙作为可回收有机催化剂的非均相载体

  摘要：

  用叠氮基表面官能化的碳酸钙颗粒的受控合成及其随后的带有炔烃锚定基的有机催化剂与铜催化的炔-叠氮化物环加成反应（CuAAC）允许制备新型的催化材料。以此方式制备的碳酸钙负载的α，α-二芳基脯氨醇甲硅烷基醚以非常高的非对映和对映选择性催化醛向反式-β-硝基苯乙烯的迈克尔加成。固定的催化剂可以通过简单的倾析法回收并重复使用。此外，这种非均相催化系统还可以适用于连续流操作，与分批工艺相比，生产率提高了五倍。

  DOI：

  10.1016/j.jcat.2020.11.013
• 作为产物：
  描述：

  (2S,4R)-4-羟基-2-(羟基二苯基甲基)吡咯烷-1-羧酸乙酯 在 sodium hydride 、 三乙胺 、 potassium hydroxide 作用下， 以 乙醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 0.25h， 生成 (2S,4R)-2-(diphenyl((trimethylsilyl)oxy)methyl)-4-(prop-2-yn-1-yloxy)pyrrolidine
  参考文献：
  名称：

  Solid supported Hayashi–Jørgensen catalyst as an efficient and recyclable organocatalyst for asymmetric Michael addition reactions

  摘要：

  A comparison of three different catalytic systems for the efficient, asymmetric synthesis of N-({(3R,4R)-4-[(benzyloxy)methyllpyrrolidin-3-yl]methyl)-N-(2-methylpropyl)benzenesulfonamide 1 (BZN) is described. The presented strategy is based on the organocatalytic Michael addition of aldehyde 2 to trans-nitroalkene 3, and subsequent reductive cyclization. High yields, enantio-, and diastereoselectivities were achieved in the Michael addition by application of a POSS- or Wang resin-supported Hayashi-Jorgensen catalyst. (C) 2017 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2017.10.016
• 作为试剂：
  描述：

  顺-1,4-二苄氧基-2-丁烯 在 (2S,4R)-2-(diphenyl((trimethylsilyl)oxy)methyl)-4-(prop-2-yn-1-yloxy)pyrrolidine 、 臭氧 、 溶剂黄146 、 苯甲酸 、 锌 、 四甲基胍 作用下， 以 甲醇 、 氘代氯仿 、 二氯甲烷 、 甲苯 为溶剂， 反应 74.92h， 生成 (3R,4S)-3-((benzyloxy)methyl)-4-((N-isobutylphenylsulfonamido)methyl)-3,4-dihydro-2H-pyrrole 1-oxide 、 (3R,4R)-3-((benzyloxy)methyl)-4-((N-isobutylphenylsulfonamido)methyl)-3,4-dihydro-2H-pyrrole 1-oxide
  参考文献：
  名称：

  Solid supported Hayashi–Jørgensen catalyst as an efficient and recyclable organocatalyst for asymmetric Michael addition reactions

  摘要：

  A comparison of three different catalytic systems for the efficient, asymmetric synthesis of N-({(3R,4R)-4-[(benzyloxy)methyllpyrrolidin-3-yl]methyl)-N-(2-methylpropyl)benzenesulfonamide 1 (BZN) is described. The presented strategy is based on the organocatalytic Michael addition of aldehyde 2 to trans-nitroalkene 3, and subsequent reductive cyclization. High yields, enantio-, and diastereoselectivities were achieved in the Michael addition by application of a POSS- or Wang resin-supported Hayashi-Jorgensen catalyst. (C) 2017 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2017.10.016

文献信息

• Functionalization of Fe3O4 magnetic nanoparticles for organocatalytic Michael reactions
  作者：Paola Riente、Carolina Mendoza、Miquel A. Pericás

  DOI：10.1039/c1jm10535c

  日期：——

  (S)-α,α-Diphenylprolinol trimethylsilyl ether supported onto well-defined (5.7 ± 1.1 nm) superparamagnetic Fe3O4 nanoparticles was used as a highly active, magnetically recoverable and reusable catalyst for the asymmetric, organocatalytic Michael addition of propanal to nitroolefins leading to high enantioselectivities. The assembly of the catalytic functional nanoparticles involves two successive steps: (i) introduction of a 3-azidopropyl unit through the formation of Si–O bonds, and (ii) integration of the organocatalytic unit by means of a copper-catalysed alkyne–azide cycloaddition reaction leading to a 1,2,3-triazole linker. Neither the process of nanoparticle assembly nor its catalytic use in dichloromethane solution provokes particle growth or agglomeration, this behaviour being key for the observation of high catalytic activity and for recyclability.

  (S)-α,α-二苯基丙醇内酰胺三甲基硅醚负载于定义良好的（5.7 ± 1.1 纳米）超顺磁性Fe3O4纳米粒子上，被用作一种高活性、磁性可回收和可重复使用的催化剂，用于不对称有机催化米克尔加成反应，其中丙醛与硝基烯烃加成，得到高对映选择性产物。催化功能纳米粒子的组装涉及两个连续步骤：（i）通过形成Si–O键引入3-叠氮丙基单元，以及（ii）通过铜催化的炔烃-叠氮环加成反应将有机催化单元整合到1,2,3-三唑连接子上。无论是在纳米粒子组装过程中还是在二氯甲烷溶液中的催化使用过程中，都不会引发粒子生长或聚集，这种行为对于观察到高催化活性和可回收性至关重要。
• Polystyrene-Supported Diarylprolinol Ethers as Highly Efficient Organocatalysts for Michael-Type Reactions
  作者：Esther Alza、Sonia Sayalero、Pinar Kasaplar、Diana Almaşi、Miquel A. Pericàs

  DOI：10.1002/chem.201101730

  日期：2011.10.4

  addition of aldehydes to nitroolefins and of malonates or nitromethane to α,β‐unsaturated aldehydes. The combination of the catalytic unit, the triazole linker, and the polymeric matrix provides unprecedented substrate selectivity, in favor of linear, short‐chain aldehydes, when the organocatalyzed reaction proceeds by an enamine mechanism. High versatility is noted in reactions that proceed via an iminium

  锚固在聚苯乙烯树脂上的α，α-二苯基脯氨醇甲基和三甲基甲硅烷基醚是通过铜催化的叠氮化物-炔烃环加成反应（CuAAC）制备的。O显示的催化活性和对映选择性三甲基甲硅烷基衍生物与最著名的均相催化剂表现出的可比性相当，后者可将醛加成到硝基烯烃中，将丙二酸酯或硝基甲烷加成到α，β-不饱和醛上。当有机催化的反应通过烯胺机制进行时，催化单元，三唑连接基和聚合物基体的组合可提供前所未有的底物选择性，有利于线性短链醛。通过亚胺离子中间体进行的反应具有很高的通用性。还通过不对称迈克尔加成反应评估了聚苯乙烯负载的α，α-二苯基脯氨醇甲醚的催化行为。通常，将二芳基脯氨醇醚固定在不溶性聚苯乙烯树脂上的CuAAC具有重要的操作优势，例如高催化活性，
• A Highly Selective, Polymer-Supported Organocatalyst for Michael Additions with Enzyme-Like Behavior
  作者：Esther Alza、Miquel A. Pericàs

  DOI：10.1002/adsc.200900817

  日期：2009.12

  A polymer-supported α,α-diarylprolinol silyl ether displays catalytic activity and enantioselectivity comparable to the best homogeneous catalysts in the Michael addition of aldehydes to nitroolefins. Above all, the combination of polymer backbone, triazole linker, and catalytic unit confers to it an unprecedented substrate selectivity in favor of linear, short-chain aldehydes.

  聚合物负载的α，α-二芳基脯氨醇甲硅烷基醚显示出与醛中的迈克尔加成至硝基烯烃的最佳均相催化剂相当的催化活性和对映选择性。最重要的是，聚合物主链，三唑连接基和催化单元的组合赋予了其空前的底物选择性，有利于线性，短链醛。
• Efficient, Enantioselective Iminium Catalysis with an Immobilized, Recyclable Diarylprolinol Silyl Ether Catalyst
  作者：Ina Mager、Kirsten Zeitler

  DOI：10.1021/ol100166z

  日期：2010.4.2

  A highly efficient approach for the synthesis, application, and recycling of immobilized diarylprolinol silyl ethers was developed. The MeOPEG-supported Jørgensen−Hayashi catalyst provides unchanged reactivity and selectivity as compared to the homogeneous catalyst, as demonstrated for the Michael addition of nitromethane to α,β-unsaturated aldehydes via iminium activation. In addition, the immobilization

  开发了一种高效的固定化二芳基脯氨醇甲硅烷基醚的合成，应用和回收方法。与均相催化剂相比，MeOPEG负载的Jørgensen-Hayashi催化剂提供了不变的反应性和选择性，如通过亚胺基活化将硝基甲烷迈克尔加成到α，β-不饱和醛上所证明的。另外，固定化使得可以简单，无柱地分离纯净的，敏感的醛产物，因此对于在更复杂的合成中的应用可能是有用的。
• A Visible‐Light‐Powered Polymerization Method for the Immobilization of Enantioselective Organocatalysts into Microreactors
  作者：Rico Warias、Daniele Ragno、Alessandro Massi、Detlev Belder

  DOI：10.1002/chem.202002063

  日期：2020.10.15

  A versatile one‐step photopolymerization approach for the immobilization of enantioselective organocatalysts is presented. Chiral organocatalyst‐containing monoliths based on polystyrene divinylbenzene copolymer were generated inside channels of microfluidic chips. Exemplary performance tests were performed for the monolithic Hayashi–Jørgensen catalyst in continuous flow, which showed good results

  提出了一种用于固定对映选择性有机催化剂的通用的一步光聚合方法。在微流控芯片的通道内生成了基于聚苯乙烯二乙烯基苯共聚物的手性有机催化剂整料。对整块Hayashi–Jrrgensen催化剂进行连续流的示例性性能测试，结果表明，就立体选择性和催化剂稳定性而言，在仅消耗最少的试剂和溶剂的情况下，将迈克尔迈克尔加成至硝基烯烃即可。