(2S,5R)-2-methyl-5-phenylpyrrolidine

• 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: (2S,5R)-2-methyl-5-phenylpyrrolidine
• 英文别名: trans-2-methyl-5-phenylpyrrolidine
• 化学式: C₁₁H₁₅N
• 分子量: 161.247
• InChiKey: FTUSZADPSPPGFA-GXSJLCMTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  1-苯基-1,4-戊二酮 在 glucose dehydrogenase 、 ammonia borane 、 D-葡萄糖 、 L-丙氨酸 、 磷酸吡哆醛 、 pseudogulbenkiania ferrooxidans transaminase 、 nicotinamide adenine dinucleotide 、 L-lactate dehydrogenase 作用下， 以 二甲基亚砜 为溶剂， 反应 48.0h， 生成 (2S,5R)-2-methyl-5-phenylpyrrolidine
  参考文献：
  名称：

  用于合成手性 2,5-二取代吡咯烷的区域选择性和立体选择性 ω-转氨酶/单胺氧化酶级联反应

  摘要：

  从简单的非手性结构单元开始合成光学纯手性胺的生物催化方法是非常理想的，因为这些基序存在于多种重要的天然产物和药物化合物中。本文报道了一种用于合成手性 2,5-二取代吡咯烷的新型一锅 ω-转氨酶 (TA)/单胺氧化酶 (MAO-N) 级联工艺。反应以优异的对映选择性和非对映选择性（>94 % ee；>98 % de) 并且可以在制备规模上进行。该方法利用两种酶显示的互补区域选择性和立体选择性，确保转氨酶建立的立体中心不受单胺氧化酶的影响，并突出了这种多酶级联在有效合成手性构件方面的潜力。

  DOI：

  10.1002/anie.201309208

文献信息

• 3,3‘-Bis(trisarylsilyl)-Substituted Binaphtholate Rare Earth Metal Catalysts for Asymmetric Hydroamination
  作者：Denis V. Gribkov、Kai C. Hultzsch、Frank Hampel

  DOI：10.1021/ja058287t

  日期：2006.3.1

  Chiral 3,3'-bis(trisarylsilyl)-substituted binaphtholate rare earth metal complexes (R)-[LnBinol-SiAr3}(o-C6H4CH2NMe2)(Me2NCH2Ph)] (Ln = Sc, Lu, Y; Binol-SiAr3 = 3,3'-bis(trisarylsilyl)-2,2'-dihydroxy-1,1'-binaphthyl; Ar = Ph (2-Ln), 3,5-xylyl (3-Ln)) and (R)-[LaBinol-Si(3,5-xylyl)3}E(SiMe3)2}(THF)2] (E = CH (4a), N (4b)) are accessible via facile arene, alkane, and amine elimination. They are efficient

  手性 3,3'-双(三芳基甲硅烷基)-取代的联萘金属络合物 (R)-[LnBinol-SiAr3}(o-C6H4CH2NMe2)(Me2NCH2Ph)] (Ln = Sc, Lu, Y; Binol-SiAr3 = 3,3'-双(三芳基甲硅烷基)-2,2'-二羟基-1,1'-联萘；Ar = Ph (2-Ln)、3,5-二甲苯基 (3-Ln)) 和 (R)-[ LaBinol-Si(3,5-二甲苯基)3}E(SiMe3)2}(THF)2] (E = CH (4a), N (4b)) 可通过芳烃、烷烃和胺轻松消除. 它们是氨基烯烃不对称加氢胺化/环化的有效催化剂，使用 (R)-2- 在 25 摄氏度下为 2,2-二苯基-戊-4-烯胺 (5c) 提供高达 840 h(-1) 的 TOF Y。在 5c 与 (R)-2-Sc 的环化中实现了高达 95% ee 的对映选择性。反应显示出明显的零级
• DIRECT C-H AMINATION AND AZA-ANNULATION
  申请人：The Board of Regents of the University of Texas System

  公开号：US20190152892A1

  公开（公告）日：2019-05-23

  In some aspects, the present disclosure provides methods of aminating an aromatic compound comprising reacting an aminating agent with an aromatic compound in the presence of a rhodium catalyst. In some embodiments, the methods may comprise aminating an aromatic compound which contains multiple different functional groups. The methods described herein may also be used to create bicyclic system comprising reacting an intramolecular aminating agent with an aromatic ring to obtain a second ring containing a nitrogen atom. In another aspect, the methods described herein may also be used to create a cyclic aliphatic cyclic/poly cyclic amine system comprising a reacting an intramolecular aminating agent by insertion into a C(sp3)-H bond.

  在某些方面，本公开提供了一种芳香化合物胺化的方法，包括在铑催化剂存在下，将胺化剂与芳香化合物反应。在某些实施例中，这些方法可能包括胺化含有多种不同功能基团的芳香化合物。本文描述的方法还可用于创建包含在芳香环中通过反应分子内胺化剂获得含氮原子的第二环的双环系统。在另一方面，本文描述的方法还可用于创建通过插入C(sp3)-H键反应分子内胺化剂的环脂环/多环胺系统。
• One-Pot Cascade Synthesis of Mono- and Disubstituted Piperidines and Pyrrolidines using Carboxylic Acid Reductase (CAR), ω-Transaminase (ω-TA), and Imine Reductase (IRED) Biocatalysts
  作者：Scott P. France、Shahed Hussain、Andrew M. Hill、Lorna J. Hepworth、Roger M. Howard、Keith R. Mulholland、Sabine L. Flitsch、Nicholas J. Turner

  DOI：10.1021/acscatal.6b00855

  日期：2016.6.3

  Access to enantiomerically pure chiral mono- and disubstituted piperidines and pyrrolidines has been achieved using a biocatalytic cascade involving carboxylic acid reductase (CAR), ω-transaminase (ω-TA), and imine reductase (IRED) enzymes. Starting from keto acids or keto aldehydes, substituted piperidine or pyrrolidine frameworks can be generated in high conversion, ee, and de in one pot, with each

  使用涉及羧酸还原酶（CAR），ω-转氨酶（ω-TA）和亚胺还原酶（IRED）的生物催化级联反应，可获得对映体纯的手性单和双取代哌啶和吡咯烷。从酮酸或酮醛开始，可以在一锅中以高转化率，ee和de生成高取代度的哌啶或吡咯烷骨架，每种生物催化剂在催化过程中均表现出化学，区域和/或立体选择性。该研究还包括对甲基环取代基位置对IRED催化手性亚胺还原的影响的系统研究。在这些反应中观察到的选择性分析表明，底物与酶控制之间存在有趣的平衡。
• Direct C—H amination and aza-annulation
  申请人：The Board of Regents of the University of Texas System

  公开号：US10995056B2

  公开（公告）日：2021-05-04

  In some aspects, the present disclosure provides methods of aminating an aromatic compound comprising reacting an aminating agent with an aromatic compound in the presence of a rhodium catalyst. In some embodiments, the methods may comprise aminating an aromatic compound which contains multiple different functional groups. The methods described herein may also be used to create bicyclic system comprising reacting an intramolecular aminating agent with an aromatic ring to obtain a second ring containing a nitrogen atom. In another aspect, the methods described herein may also be used to create a cyclic aliphatic cyclic/poly cyclic amine system comprising a reacting an intramolecular aminating agent by insertion into a C(sp3)-H bond.

  在某些方面，本公开提供了胺化芳香族化合物的方法，包括在铑催化剂存在下，胺化剂与芳香族化合物反应。在某些实施方案中，这些方法可包括胺化含有多个不同官能团的芳香族化合物。本文所述方法还可用于制造双环体系，包括使分子内胺化剂与芳香环反应，以获得含有氮原子的第二环。另一方面，本文所述方法还可用于制造环脂族环/多环胺体系，该体系包括通过插入 C(sp3)-H 键使分子内胺化剂发生反应。
• Selenium promoted synthesis of enantiopure pyrrolidines starting from chiral aminoalcohols
  作者：Marcello Tiecco、Lorenzo Testaferri、Luana Bagnoli、Catalina Scarponi、Andrea Temperini、Francesca Marini、Claudio Santi

  DOI：10.1016/j.tetasy.2007.11.003

  日期：2007.11

  Starting from commercially available enantiomerically pure aminoalcohols and using simple conversions promoted by organoselenium reagents, several enantiomerically pure substituted pyrrolidines were prepared. After double protections (R)- or (S)-2-phenylglycinols were converted into the beta-amino selenides by displacing the tosyl group with phenyl selenolate anions. The phenylseleno group was then substituted by an allyl group by treatment with allyltributyltin and AIBN. The reaction of these allylic derivatives with electrophilic phenylselenium reagents afforded selenium containing pyrrolidines as the result of a 5-exo-trig cyclization. The pyrrolidine derivatives thus obtained were reductively deselenylated with triphenyltin hydride and AIBN. Moreover, the selenides were converted into the selenones, which easily gave substitution with different nucleophiles. Enantiopure 2,5-pyrrolidines containing azido, methylthio, cyano and iodo groups were thus obtained. (c) 2007 Elsevier Ltd. All rights reserved.