(S)-2-(azidodiphenylmethyl)-1-benzylpyrrolidine | 1072028-47-7

• 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: (S)-2-(azidodiphenylmethyl)-1-benzylpyrrolidine
• 英文别名: (2S)-2-[azido(diphenyl)methyl]-1-benzylpyrrolidine
• CAS: 1072028-47-7
• 化学式: C₂₄H₂₄N₄
• 分子量: 368.481
• InChiKey: ZVZHRRJRPMMMAL-QHCPKHFHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  17.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (S)-2-(azidodiphenylmethyl)-1-benzylpyrrolidine 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 以98%的产率得到(S)-(1-benzylpyrrolidin-2-yl)diphenylmethanamine
  参考文献：
  名称：

  （-）-（2S，4R）-3'-甲氧基Cetrochlorol的立体选择性全合成：制备和使用基于脯氨酸的新型助剂用于不对称乙酸醛醇缩醛反应。

  摘要：

  证明了（-）-（2S，4R）-3′-甲氧基瓜酚和（-）-（2S，4S）-3′-甲氧基瓜酚的第一立体选择性全合成。合成了基于脯氨酸的咪唑烷酮，并将其用作不对称乙酸酯羟醛反应的手性助剂，以在目标分子中产生初始手性。通过向Weinreb的酰胺官能团中添加原位生成的二氯甲基锂来引入双基二氯甲烷功能。

  DOI：

  10.1021/acs.joc.9b03227
• 作为产物：
  描述：

  N-benzyl-(S)-proline methyl ester 在 sodium azide 、 硫酸 作用下， 以 乙醚 、 氯仿 为溶剂， 生成 (S)-2-(azidodiphenylmethyl)-1-benzylpyrrolidine
  参考文献：
  名称：

  （-）-（2S，4R）-3'-甲氧基Cetrochlorol的立体选择性全合成：制备和使用基于脯氨酸的新型助剂用于不对称乙酸醛醇缩醛反应。

  摘要：

  证明了（-）-（2S，4R）-3′-甲氧基瓜酚和（-）-（2S，4S）-3′-甲氧基瓜酚的第一立体选择性全合成。合成了基于脯氨酸的咪唑烷酮，并将其用作不对称乙酸酯羟醛反应的手性助剂，以在目标分子中产生初始手性。通过向Weinreb的酰胺官能团中添加原位生成的二氯甲基锂来引入双基二氯甲烷功能。

  DOI：

  10.1021/acs.joc.9b03227

文献信息

• Synthesis of three novel chiral diamines derived from (S)-proline and their evaluation as precursors of diazaborolidines for the catalytic borane-mediated enantioselective reduction of prochiral ketones
  作者：J. Luis Olivares-Romero、Eusebio Juaristi

  DOI：10.1016/j.tet.2008.07.080

  日期：2008.10

  15 min, air cooling) using chiral diamines derived from inexpensive and commercially available (S)-proline and borane-dimethyl sulfide. Special mention deserves the synthesis of potentially versatile diamine (S)-8 [(S)-(pyrrolidin-2-yl)diphenylmethanamine], with the key step being the conversion of tertiary alcohol (S)-(1-benzylpyrrolidin-2-yl)diphenyl methanol, (S)-12, to azide (S)-13. The chiral diazaborolidine/BH3

  使用衍生自廉价和可商购获得的（S）-脯氨酸和硼烷-二甲基的手性二胺，可以轻松地在甲苯溶剂中于75°C在微波辐射下（100 W，15分钟，空冷）原位制备一系列手性二氮杂硼烷催化剂硫化物。特别值得一提的是合成潜在的通用二胺（S）-8 [（S）-（吡咯烷-2-基）二苯基甲胺]，关键步骤是叔醇（S）-（1-苄基吡咯烷-2-的转化（S）-12的芳基）二苯基甲醇合成叠氮化物（S）-13的基团。手性二氮杂硼烷/ BH 3 试剂系统已成功用于手性酮的对映选择性还原，以优异的收率和高达96％的对映体纯度提供了相应的仲醇。
• Novel Diarylprolinol-derived Amino Perfluoroalkanesulfonamide Catalysts: Highly Enantio- and Diastereoselective Aldol Reaction
  作者：Léopold M. Lutete、Tetsuya Ikemoto

  DOI：10.1246/cl.170034

  日期：2017.4.5

  A new series of amino perfluoroalkanesulfonamide compounds derived from diarylprolinols has been developed and found to be efficient catalysts for the reaction of ethyl glyoxylate with 4-(benzyloxy)butanal. The aldol product, obtained in good yield with excellent enantio- and diastereomeric excess, is an intermediate for the synthesis of bis-THF alcohol, which is a commonly used unit in the design

  已开发出一系列衍生自二芳基脯氨醇的新系列氨基全氟烷烃磺酰胺化合物，并发现它们是乙醛酸乙酯与 4-（苄氧基）丁醛反应的有效催化剂。以良好的收率和优异的对映体和非对映体过量获得的羟醛产物是合成双四氢呋喃醇的中间体，双四氢呋喃醇是设计 HIV 蛋白酶抑制剂（如达芦那韦）的常用单元。
• Asymmetric Henry reaction catalysed by L-proline derivatives in the presence of Cu(OAc)₂: isolation and characterization of an<i>in situ</i>formed Cu(II) complex
  作者：H. Atoholi Sema、Ghanashyam Bez、Sanjib Karmakar

  DOI：10.1002/aoc.3123

  日期：2014.4

  by the Henry reaction is one of the most exploited carbon–carbon bond‐forming reactions owing to the versatility of both functional groups for synthetic manipulation by functional group interconversion. Here we report synthesis of a series of proline‐derived compounds to study their catalytic activities for asymmetric Henry reaction in the presence of Cu(OAc)2.H2O. The proline derivative, 2‐((E)‐(((

  亨利反应合成不对称β-硝基醇是利用最多的碳-碳键形成反应之一，这是由于两个官能团都具有多功能性，可以通过官能团相互转化进行合成操作。在这里我们报告了一系列脯氨酸衍生的化合物的合成，以研究它们在Cu（OAc）2 .H 2 O存在下对不对称亨利反应的催化活性。脯氨酸衍生物2 ‐（（E）‐（（（S）-1-苄基吡咯烷基）二苯基甲基亚氨基）甲基）苯酚1表现出最佳的催化活性。原位形成的催化物种Cu（II）-1配合物被分离，并通过各种光谱技术和X射线晶体学表征，显示出顺式‐N 2 O 2协调几何。与大多数已报道的方案不同，无需使用添加碱即可获得不对称的β-硝基醇。版权所有©2014 John Wiley＆Sons，Ltd.
• In search of diamine analogs of the α,α-diphenyl prolinol privileged chiral organocatalyst. Synthesis of diamine derivatives of α,α-diphenyl-(S)-prolinol and their application as organocatalysts in the asymmetric Michael and Mannich reactions
  作者：Gloria Reyes-Rangel、Jorge Vargas-Caporali、Eusebio Juaristi

  DOI：10.1016/j.tet.2015.11.032

  日期：2016.1

  This paper describes improved reaction conditions for the substitution of the hydroxyl group in (S)-diphenyl(pyrrolidin-2-yl)methanol by the azide group, which was then reduced to the diamine derivative. We examined two protecting groups (N-Bn and N-Boc) on the pyrrolidine nitrogen in order to functionalize the primary amino group into various amide, alkylated amine, sulfonamide, thiourea and triazole derivatives. Notably, carefully controlled conditions were required to generate the desired derivatives from the sterically hindered benzhydrylamine moiety. Unexpectedly, upon removal of the N-protecting group in derivatives containing electrophilic polar double bonds (C=S, C=O) cyclization took place, affording products such as amidines. The target compounds were evaluated as bifunctional organocatalysts in the asymmetric Michael and Mannich addition reactions. (S)-2-(Azidodiphenylmethyl) pyrrolidine (S)-7 was identified as the most efficient organocatalyst among the various diamine derivatives of alpha,alpha-diphenyl-(S)-prolinol prepared in this work. (C) 2015 Elsevier Ltd. All rights reserved.
• Synthesis of chiral 2-(anilinophenylmethyl)pyrrolidines and 2-(anilinodiphenylmethyl)pyrrolidine and their application to enantioselective borane reduction of prochiral ketones as chiral catalysts
  作者：Naoya Hosoda、Hideaki Kamito、Miki Takano、Yoshitaka Takebe、Yoshitaka Yamaguchi、Masatoshi Asami

  DOI：10.1016/j.tet.2012.12.024

  日期：2013.2

  Chiral diamines, 2-(anilinophenylmethyl)pyrrolidines and 2-(anilinodiphenylmethyl)pyrrolidine, were prepared from N-(tert-butoxycarbonyl)pyrrolidine or (S)-proline as a starting material, respectively. These chiral diamines were efficient for the catalytic enantioselective borane reduction of acetophenone. Using (S)-2-(anilinodiphenylmethyl)pyrrolidine, chiral secondary alcohols were obtained from prochiral ketones with good to excellent enantiomeric excesses (up to 98% ee). (C) 2012 Elsevier Ltd. All rights reserved.