(R)-benzyl 4-(3-acryloyloxy-4,4-dimethyl-2-oxopyrrolidin-1-yl)-benzoate | 777088-07-0

• 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: (R)-benzyl 4-(3-acryloyloxy-4,4-dimethyl-2-oxopyrrolidin-1-yl)-benzoate
• 英文别名: (R)-benzyl 4-(3-acryloyloxy-4,4-dimethyl-2-oxopyrrolidin-1-yl)benzoate；(R)-benzyl-4-(3-acryloyloxy-4,4-dimethyl-2-oxopyrrolidin-1-yl)benzoate；benzyl (R)-4-(3-acryloyloxy-4,4-dimethyl-2-oxopyrrolidin-1-yl)benzoate；benzyl 4-[(3R)-4,4-dimethyl-2-oxo-3-prop-2-enoyloxypyrrolidin-1-yl]benzoate
• CAS: 777088-07-0
• 化学式: C₂₃H₂₃NO₅
• 分子量: 393.439
• InChiKey: DGTOKEYZGVNADP-FQEVSTJZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  29
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  72.9
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (R)-benzyl 4-(3-acryloyloxy-4,4-dimethyl-2-oxopyrrolidin-1-yl)-benzoate 在 lithium hydroxide 、 水 作用下， 以 四氢呋喃 、 水 、 甲苯 为溶剂， 反应 29.0h， 生成 (R)-4-(3-hydroxy-4,4-dimethyl-2-oxopyrrolidin-1-yl) benzoic acid
  参考文献：
  名称：

  (R)-(4-(Benzyloxycarbonylphenyl)-3-hydroxy-4,4-dimethyl-2-pyrrolidinone) acrylate derivative as a chiral dienophile for the synthesis of enantiopure 2-aminocyclohexane carboxylic acids

  摘要：

  An asymmetric Diels-Alder reaction between the enantiopure (R)-benzyl-4-(3-acryloyloxy-4,4-dimethyl-2-oxopyrrolidin-1-yl)-benzoate (R)-2 and the N-Z-aminodiene 3 proceeded with total endo diastereoselectivity and was facially controlled in favour of the (3'R,1R,2S)-adduct. The two adducts obtained, 4 (the main compound) and 5, were isolated pure after Column chromatography on silica gel. Their LiOH hydrolysis followed by palladium-catalyzed hydrogenation of the double bond concomitant with hydrogenolysis of the carbamate moiety yielded the enantiopure cis-2-aminocyclohexane carboxylic acids (1R,2S)-8 and (1S,2R)-8. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2005.05.024
• 作为产物：
  描述：

  (1S,3'R)-[1-(4-benzyloxycarbonylphenyl)-4,4-dimethyl-2-oxopyrrolidin-3-yl] 4,7,7-trimethyl-3-oxo-2-oxabicyclo[2.2.1]heptane-1-carboxylate 在 lithium hydroxide 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 1.5h， 生成 (R)-benzyl 4-(3-acryloyloxy-4,4-dimethyl-2-oxopyrrolidin-1-yl)-benzoate
  参考文献：
  名称：

  （R）-或（S）-4-（3-羟基-4,4-二甲基-2-氧吡咯烷-1-基）苯甲酸作为固相不对称Diels-Alder反应的新手性助剂

  摘要：

  描述了对映体纯（R）-和（S）-4-（3-羟基-4,4-二甲基-2-氧吡咯烷-1-基）苯甲酸的合成，并使用了相应的负载型手性丙烯酸酯衍生物不同二烯在固相不对称Diels-Alder反应中的亲双烯体。在所有情况下，反应均以高收率和高区域选择性或内切选择性提供了预期的化合物。此外，使用2,3-二甲基丁二烯，环戊二烯或1,3-环己二烯可获得较高的面部非对映选择性（86-99％de）。相反，异戊二烯观察到低至中等的面部非对映选择性（40-76％de），具体取决于所使用的聚合物。

  DOI：

  10.1016/j.tetasy.2004.06.012

文献信息

• Asymmetric Diels–Alder Reaction of Aminodienes with a Nonracemic Acrylate Bound to Rink Resin: A Comparison of These Reactions with Their Solution-State Analogues
  作者：Olivier Songis、Pierre Yves Géant、Guillaume Sautrey、Jean Martinez、Monique Calmès

  DOI：10.1002/ejoc.200700677

  日期：2008.1

  derivatives and three N-Z-protected 1-aminodienes have been investigated both in solution and on a solid support. Comparable results for each reaction were observed with the formation of the corresponding constrained cyclic s-amino acids in high yield and moderate-to-good selectivity when using optimized conditions. A detailed comparison of both solution and solid-support synthesis by conventional heating

  (3R)-4,4-二甲基-2-氧代吡咯烷-3-基丙烯酸酯衍生物和三个 NZ 保护的 1-氨基二烯之间的不对称 Diels-Alder 反应已在溶液和固体载体上进行了研究。观察到每个反应的可比结果，在使用优化条件时，以高产率和中等至良好的选择性形成相应的受限环状 s-氨基酸。通过常规加热和微波活化对溶液和固体载体合成的详细比较表明，微波技术通常具有优势。我们还证明了在固体支持物上的反应很好地解决了试剂的低反应性和不稳定性问题。
• Asymmetric Diels–Alder Cycloaddition of 1-Aminocyclohexadiene to Chiral Acrylate: Synthesis of Enantiopure Bridgehead-Aminobicyclo[2.2.2]octane-2-carboxylic Acid Derivatives
  作者：Olivier Songis、Claude Didierjean、Camille Laurent、Jean Martinez、Monique Calmès

  DOI：10.1002/ejoc.200700236

  日期：2007.7

  2R,4R)-1-(benzyloxycarbonylamino)bicyclo[2.2.2]oct-5-ene-2-carboxylic acid [(1S,2R,4R)-4], (1R,2R,4S)-1-(benzyloxycarbonylamino)bicyclo[2.2.2]oct-5-ene-2-carboxylic acid [(1R,2R,4S)-5] and (R)-1-aminobicyclo[2.2.2]octane-2-carboxylic acid [(R)-6]. This work has led to the preparation of these enantiopure bicyclic β-amino acids and provides a rare example of an asymmetric Diels–Alder reaction by microwave

  (R)-4-(3-羟基-4,4-二甲基-2-氧代吡咯烷-1-基)苯甲酸苄酯(R)-2的丙烯酸酯衍生物与1-(苄氧羰基氨基)环己二烯3在微波下反应在无溶剂条件下进行辐照，以良好的产率 (91%) 产生 [4+2] 环加合物。反应以中等内向选择性 (67%) 和良好的面部选择性 (90%) 进行。分离并转化主要的环加合物以提供三种对映体纯双环 β-氨基酸：(1S,2R,4R)-1-(苄氧羰基氨基)双环[2.2.2]oct-5-ene-2-羧酸[(1S, 2R,4R)-4], (1R,2R,4S)-1-(benzyloxycarbonylamino)bicyclo[2.2.2]oct-5-ene-2-羧酸 [(1R,2R,4S)-5] 和 ( R)-1-氨基双环[2.2.2]辛烷-2-羧酸[(R)-6]。这项工作导致了这些对映体纯双环 β-氨基酸的制备，并提供了通过微波活化进行不对称 Diels-Alder
• New 1,3-amino alcohols derived from enantiopure bridgehead β-aminobicyclo[2.2.2]oct-5-ene-2-carboxylic acids
  作者：Christophe André、Monique Calmès、Françoise Escale、Muriel Amblard、Jean Martinez、Olivier Songis

  DOI：10.1007/s00726-011-1097-6

  日期：2012.7

  Constrained enantiopure bicyclic β-amino acids derived from the asymmetric Diels–Alder reaction of the (R)-benzyl-4-(3-acryloyloxy-4,4-dimethyl-2-oxopyrrolidin-1-yl)-benzoate and the 1-(benzyloxycarbonylamino)cyclohexadiene provide original templates for the construction of new rigid enantiopure 1,3-amino alcohols.

  （R）-苄基-4-（3-丙烯酰氧基-4,4-二甲基-2-氧吡咯烷-1-基）-苯甲酸酯和1-的不对称Diels-Alder反应衍生的受约束的对映体纯的双环β-氨基酸（苄氧羰基氨基）环己二烯为构建新的刚性对映纯1，3-氨基醇提供了原始模板。
• Asymmetric Diels–Alder reaction using a new chiral β-nitroacrylate for enantiopure trans-β-norbornane amino acid preparation
  作者：Monique Calmès、Françoise Escale、Claude Didierjean、Guillaume Cazals、Jean Martinez

  DOI：10.1016/j.tetasy.2007.10.001

  日期：2007.10

  The main nitronorbornene adduct derived from the asymmetric Diels-Alder reaction of (S)-benzyl-4-(3-(3-nitroacryloyloxy)-4,4- dimethyl-2-oxopyrrolidin-1-yl) benzoate (S)-1 and cyclopentadiene was isolated and transformed to afford the enantiopure bicyclic beta-amino acid (1S,2R,3R,4R)-trans-beta-norbornane amino acid 9. The enantiomer (1R,2S,3S,4S)-9 could be obtained by the same synthetic route by using the chiral auxiliary (R)-1. (c) 2007 Elsevier Ltd. All rights reserved.
• Asymmetric Baylis–Hillman reactions using (R)-4-(3-hydroxy-4,4-dimethyl-2-oxopyrrolidin-1-yl) benzoic acid acrylate derivatives in solution and on solid support
  作者：Monique Calmès、Rhalid Akkari、Nicolas Barthes、Françoise Escale、Jean Martinez

  DOI：10.1016/j.tetasy.2005.05.016

  日期：2005.6

  The influence of several variables on the course of the Baylis-Hillman reaction between the (R)-4-(3-hydroxy-4,4dimethyl-2-oxopyrrolidin-1-yl) benzoic acid acrylate derivatives (R)-2 and (R)-3 and aromatic aldehydes has been investigated both in solution and on solid support: these resulted in comparable results with the formation or adducts in high yield and moderate selectivity. (c) 2005 Elsevier Ltd. All rights reserved.