(+)-(R)-1-tert-Butoxycarbonyl-4-phenyl-2-pyrrolidinone

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: (+)-(R)-1-tert-Butoxycarbonyl-4-phenyl-2-pyrrolidinone
• 英文别名: tert-butyl (R)-4-phenyl-2-oxopyrrolidine-1-carboxylate；(R)-tert-butyl 2-oxo-4-phenylpyrrolidine-1-carboxylate；(R)-1-Boc-4-phenylpyrrolidin-2-one；tert-butyl (4R)-2-oxo-4-phenylpyrrolidine-1-carboxylate
• 化学式: C₁₅H₁₉NO₃
• 分子量: 261.321
• InChiKey: JDQMEVMXXNZCHG-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+)-(R)-1-tert-Butoxycarbonyl-4-phenyl-2-pyrrolidinone 在 lithium hydroxide 作用下， 以 四氢呋喃 为溶剂， 反应 1.5h， 以89%的产率得到N-(tert-butoxycarbonyl)-β²-homophenylalanine
  参考文献：
  名称：

  Resolution of 4-Phenyl-2-pyrrolidinone: A Versatile Synthetic Intermediate

  摘要：

  描述了4-苯基-2-吡咯烷酮的分离。所得到的对映纯的吡咯烷酮被用作3-苯基吡咯烷和3-苯基-γ-氨基酸（4-氨基-3-苯基丁酸衍生物）的前体。

  DOI：

  10.1055/s-1991-26638
• 作为产物：
  描述：

  丙二酸,(氰基苯基甲基)-,二乙基酯 在 Raney-Ni W-28 盐酸 、 4-二甲氨基吡啶 、 氢氧化钾 、 氢气 、 1-羟基苯并三唑 、 三乙胺 、 N,N'-二环己基碳二亚胺 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 为溶剂， 55.0 ℃ 、405.3 kPa 条件下， 反应 55.0h， 生成 (+)-(R)-1-tert-Butoxycarbonyl-4-phenyl-2-pyrrolidinone
  参考文献：
  名称：

  Resolution of 4-Phenyl-2-pyrrolidinone: A Versatile Synthetic Intermediate

  摘要：

  描述了4-苯基-2-吡咯烷酮的分离。所得到的对映纯的吡咯烷酮被用作3-苯基吡咯烷和3-苯基-γ-氨基酸（4-氨基-3-苯基丁酸衍生物）的前体。

  DOI：

  10.1055/s-1991-26638

文献信息

• Highly Enantioselective Synthesis of Chiral γ-Lactams by Rh-Catalyzed Asymmetric Hydrogenation
  作者：Qiwei Lang、Guoxian Gu、Yaoti Cheng、Qin Yin、Xumu Zhang

  DOI：10.1021/acscatal.8b00827

  日期：2018.6.1

  a (ZhaoPhos) catalytic system has been identified for the straightforward asymmetric synthesis of chiral γ-lactams. A variety of NH free α,β-unsaturated lactams bearing a β-aryl or β-alkyl substituent were smoothly hydrogenated to provide the desired γ-lactams in up to 99% yield and 99% enantiomeric excess (ee). This methodology provides a highly practical pathway to synthesize chiral γ-lactams or

  Rh /双膦-硫脲（ZhaoPhos）催化体系已被确定用于手性γ-内酰胺的直接不对称合成。将各种带有β-芳基或β-烷基取代基的无NH的α，β-不饱和内酰胺平滑氢化，以提供所需的γ-内酰胺，产率高达99％，对映体过量（ee）高达99％。该方法提供了合成手性γ-内酰胺或γ-氨基酸的高度实用的途径。
• Enantioselective synthesis of β-aryl-γ-lactam derivatives via Heck–Matsuda desymmetrization of <i>N</i>-protected 2,5-dihydro-1<i>H</i>-pyrroles
  作者：Arnaldo G de Oliveira、Martí F Wang、Rafaela C Carmona、Danilo M Lustosa、Sergei A Gorbatov、Carlos R D Correia

  DOI：10.3762/bjoc.20.84

  日期：——

  Abstract We report herein an enantioselective palladium-catalyzed Heck–Matsuda reaction for the desymmetrization of N-protected 2,5-dihydro-1H-pyrroles with aryldiazonium salts, using the chiral N,N-ligand (S)-PyraBox. This strategy has allowed straightforward access to a diversity of 4-aryl-γ-lactams via Heck arylation followed by a sequential Jones oxidation. The overall method displays a broad scope

   抽象的 我们在此报道了一种对映选择性钯催化的 Heck-Matsuda 反应，使用手性N , N-配体 ( S )-PyraBox，用芳基重氮盐对N-保护的 2,5-二氢-1H-吡咯进行去对称化。该策略允许通过 Heck 芳基化和随后的琼斯氧化直接获得多种 4-芳基-γ-内酰胺。整个方法显示出广泛的范围和良好的对映选择性，有利于( R )对映体。选择性磷酸二酯酶 4 抑制剂咯利普兰和商业药物巴氯芬盐酸盐的有效对映选择性合成突出了该方案的适用性。 Beilstein J. Org. Chem. 2024, 20, 940–949. doi:10.3762/bjoc.20.84
• The synthesis of aracemic 4-substituted pyrrolidinones and 3-substituted pyrrolidines. An asymmetric synthesis of (-)-rolipram
  作者：A. I. Meyers、Lawrence Snyder

  DOI：10.1021/jo00053a012

  日期：1993.1

  Conjugate additions of RCuCNLi to the chiral alpha,beta-unsaturated lactam 4 gives almost exclusive exo addition-a reversal in stereochemistry when cuprates were added to chiral lactam 1. The lactams 5 were transformed into 4-substituted pyrrolidinones 8 via a three-step sequence which involved decarbalkoxylation, silane reduction and metal-ammonia benzylamine cleavage. The chemical yields as well as the enantiomeric purity were very high for this process. As an example of the usefulness of this scheme, the antidepressant (-)-Rolipram was prepared in good overall yield. Furthermore, the bicyclic lactams 6 were readily transformed, using alane as the reducing agent, to 3-substituted pyrrolidines 11. Absolute configurations of 8 and 11 were confirmed by comparison with literature assignments which also gave strong support to the facial addition of the cuprates to 4.
• Rh–IndOlefOx catalyzed conjugate addition/Heck-type coupling of organoboronics to a lactam or a lactone
  作者：Noora Kuuloja、Matti Vaismaa、Robert Franzén

  DOI：10.1016/j.tet.2012.01.040

  日期：2012.3

  Four indole-olefin-oxazoline (IndOlefOx) ligands were synthesized and evaluated in Rh-catalyzed reactions between organoboronics and a lactam or a lactone. In addition to the expected conjugate addition products, the formation of significant amounts of Heck-type products was observed. The scope and limitations of these reactions were investigated. (C) 2012 Elsevier Ltd. All rights reserved.
• Asymmetric Synthesis of β-Substituted γ-Lactams via Rhodium/Diene-Catalyzed 1,4-Additions: Application to the Synthesis of (<i>R</i>)-Baclofen and (<i>R</i>)-Rolipram
  作者：Cheng Shao、Hong-Jie Yu、Nuo-Yi Wu、Ping Tian、Rui Wang、Chen-Guo Feng、Guo-Qiang Lin

  DOI：10.1021/ol103054a

  日期：2011.2.18

  An efficient rhodium/diene-catalyzed asymmetric addition of arylboronic acids to alpha,beta-unsaturated gamma-lactams has been developed. The power of this methodology is further demonstrated by the concise synthesis of (R)-baclofen and (R)-rolipram.