(S)-2-nitro-1-phenyl-N-tosylethanamine

• 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-nitro-1-phenyl-N-tosylethanamine
• 英文别名: (S)-4-methyl-N-(2-nitro-1-phenylethyl)benzenesulfonamide；4-methyl-N-[(1S)-2-nitro-1-phenylethyl]benzenesulfonamide
• 化学式: C₁₅H₁₆N₂O₄S
• 分子量: 320.369
• InChiKey: YDXNGGZHMNMXKF-OAHLLOKOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  100
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (S)-2-nitro-1-phenyl-N-tosylethanamine 在 palladium on activated charcoal 、 氢气 、 magnesium 作用下， 以 甲醇 、 乙醇 、 水 为溶剂， 反应 0.83h， 生成 左旋咪唑
  参考文献：
  名称：

  Enantioselective aza-Henry reaction for the synthesis of (S)-levamisole using efficient recyclable chiral Cu(II)–amino alcohol derived complexes

  摘要：

  Chiral Cu(II) complexes were generated in situ by the interaction of aminoalcohol based ligands L-1-L-6 derived from (1R,2S)-(-)-2-aminodiphenylethanol, (1R,25)-1-amino-2,3-dihydro-1H-inden-2-ol, (R or S)-valinol and (S)-2-amino-1,1-diphenylpropan-1-ol with 4-tert-butyl-2,6-diformylphenol and screened for aza-Henry reaction of a variety of aromatic, aliphatic N-tosylaldimine and aromatic N-benzenesulfonamide aldimine in toluene at RT. Excellent enantioselectivity, diastereoselectivity (99%) of beta-nitro-N-tosylaldamine with good yield (80%) was achieved in case of complex L-2-Cu(II) with low catalyst loading. The enantio-pure aza-Henry product obtained was straightforwardly transformed into the enantioenriched chiral vicinal diamine (ee; 96%) with good yield in successive two steps and was further used for the synthesis of (S)-levamisole (an anthelminthic agent). The catalytic system worked well up to five cycles with retention of enantioselectivity. (C) 2015 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcata.2015.08.009
• 作为产物：
  描述：

  硝基甲烷 、 N-亚苄基-4-甲基苯磺酰胺 在 4-tert-butyl-2,6-bis[[(1S,2R)-2-hydroxy-1,2-diphenylethyl]iminomethyl]phenol 、 copper(II) acetate monohydrate 作用下， 以 甲苯 为溶剂， 反应 36.0h， 以71%的产率得到(S)-2-nitro-1-phenyl-N-tosylethanamine
  参考文献：
  名称：

  Enantioselective aza-Henry reaction for the synthesis of (S)-levamisole using efficient recyclable chiral Cu(II)–amino alcohol derived complexes

  摘要：

  Chiral Cu(II) complexes were generated in situ by the interaction of aminoalcohol based ligands L-1-L-6 derived from (1R,2S)-(-)-2-aminodiphenylethanol, (1R,25)-1-amino-2,3-dihydro-1H-inden-2-ol, (R or S)-valinol and (S)-2-amino-1,1-diphenylpropan-1-ol with 4-tert-butyl-2,6-diformylphenol and screened for aza-Henry reaction of a variety of aromatic, aliphatic N-tosylaldimine and aromatic N-benzenesulfonamide aldimine in toluene at RT. Excellent enantioselectivity, diastereoselectivity (99%) of beta-nitro-N-tosylaldamine with good yield (80%) was achieved in case of complex L-2-Cu(II) with low catalyst loading. The enantio-pure aza-Henry product obtained was straightforwardly transformed into the enantioenriched chiral vicinal diamine (ee; 96%) with good yield in successive two steps and was further used for the synthesis of (S)-levamisole (an anthelminthic agent). The catalytic system worked well up to five cycles with retention of enantioselectivity. (C) 2015 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcata.2015.08.009

文献信息

• Enantioselective Henry and Aza-Henry Reaction in the Synthesis of (<i>R</i>)-Tembamide Using Efficient, Recyclable Polymeric Cu^IIComplexes as Catalyst
  作者：Anjan Das、Manoj K. Choudhary、Rukhsana I. Kureshy、Tamal Roy、Noor-ul H. Khan、Sayed H. R. Abdi、Hari C. Bajaj

  DOI：10.1002/cplu.201402078

  日期：2014.8

  Chiral copper(II) polymeric [H4]salen (salen=bis[(salicylidene)ethylenediaminato]) complexes CuII‐1–3 were generated in situ and used as efficient catalysts in the asymmetric Henry and aza‐Henry reaction of various aromatic and aliphatic aldehydes and N‐tosylimines in the presence of various nitroalkanes at room temperature (27±2 °C) for 20 hours. This group of polymeric [H4]salen complexes demonstrated

  手性铜（II）的聚合物[H 4 ]沙仑（沙仑=双[（亚水杨基）ethylenediaminato]）配合物的Cu II -1 - 3原位产生和用作在不对称亨利有效的催化剂和各种芳族的氮杂-亨利反应在室温（27±2°C）下，在各种硝基烷存在下，脂肪族醛和N-甲苯基亚胺为20小时。这组聚合的[H 4 ] salen配合物通过使用低催化剂负载量为1 mol％（相对于单体salen）的硝基甲烷，在形成β-硝基醇方面表现出优异的性能（产品收率和对映体过量 ee高达98％）单位）和高对映体诱导（ee 94％）在aza-Henry产品中；以中等产率（78％）获得了β-硝胺。该催化系统也与硝基乙烷和亨利反应的情况下1-硝基丙烷运作良好，以提供在高收率和对映选择性的相应的产品顺式非对映体。该铜II -2复杂的克水平保持其性能，并在其性能没有显著损失方便回收的八倍。Cu II -2配合物对N的对映选择性氮杂-
• New ureas containing glycosyl and diphenylphosphinyl scaffolds: synthesis and the first attempts to use them in asymmetric synthesis
  作者：Stanisław Porwański

  DOI：10.1016/j.carres.2014.04.015

  日期：2014.7

  Chiral ureas containing glycosyl and diphenylphosphinyl scaffolds were found to be an effective organocatalyst. They were synthesised in high yields by a one-pot tandem Staudinger/aza-Wittig coupling reaction. The first attempts of using them in asymmetric synthesis are presented. Yields of the Morita-Baylis-Hillman reaction were moderate with an enantiomeric excess of up to 80%.

  发现含有糖基和二苯基膦基骨架的手性脲是有效的有机催化剂。它们通过一锅串联Staudinger / aza-Wittig偶联反应以高收率合成。提出了在不对称合成中使用它们的首次尝试。Morita-Baylis-Hillman反应的产率中等，对映体过量高达80％。
• Enantioselective copper-aminopyridine-catalyzed aza-Henry reaction with chelating N-(2-pyridyl)sulfonyl imines
  作者：Gonzalo Blay、Ana Escamilla、Víctor Hernández-Olmos、José R. Pedro、Amparo Sanz-Marco

  DOI：10.1002/chir.22009

  日期：2012.6

  This article describes a copper‐catalyzed aza‐Henry reaction. Copper complexes of camphor‐derived aminopyridines catalyze the addition of nitromethane to N‐(2‐pyridyl)sulfonyl aldimines to give the corresponding β‐nitrosulfonamides with good yields and variable enantiomeric excesses (up to 83%). An example of transformation of these compounds into N‐(2‐pyridyl)sulfonyl‐α‐amino acids and deprotection

  本文介绍了铜催化的氮杂亨利反应。樟脑衍生的氨基吡啶的铜络合物催化将硝基甲烷添加到N-（2-吡啶基）磺酰基醛亚胺中，从而制得相应的β-硝基磺酰胺，其收率高且对映异构体过量（高达83％）。提供了将这些化合物转化为N-（2-吡啶基）磺酰基-α-氨基酸并用Mg-MeOH进行磺酰胺脱保护的实例。手性24：441–450，2012年。 ©2012 Wiley Periodicals，Inc.
• Enantioselective aza-Henry reaction of t-Boc protected imines and nitroalkanes with bifunctional squaramide organocatalysts
  作者：Dilşad Susam、Cihangir Tanyeli

  DOI：10.1039/c6nj04078k

  日期：——

  An organocatalytic asymmetric aza-Henry reaction of t-Boc protected imines with nitroalkanes has been established by chiral acid–base type bifunctional Cinchona alkaloid/squaramide organocatalysts. The cooperation of a quinine motif as a base and sterically encumbered squaramide (H-bond donor) enabled mostly complete conversion of a range of reactants into the corresponding aza-Henry products at room

  t - Boc保护的亚胺与硝基烷烃的有机催化不对称aza-Henry反应是通过手性酸碱型双功能金鸡纳生物碱/方酰胺有机催化剂建立的。奎宁基序作为碱和空间受限的方酰胺（氢键供体）的配合，可以在室温下以良好的选择性将一系列反应物完全转化为相应的aza-Henry产品（选择性高达91％ee，10 mol）催化剂负载百分比）。
• Highly Enantioselective Aza-Henry Reaction of <i>N</i>-Tosyl Imines Catalyzed by <i>N,N</i>‘-Dioxide−Cu(I) Complexes
  作者：Hui Zhou、Dan Peng、Bo Qin、Zongrui Hou、Xiaohua Liu、Xiaoming Feng

  DOI：10.1021/jo702200u

  日期：2007.12.1

  The N,N‘-dioxide−Cu(I) complexes have been developed to catalyze the addition of nitromethane to N-tosyl aldimines. The aza-Henry reaction proceeds smoothly affording the corresponding nitro amines in good yields with high enantioselectivities. A catalytic cycle is proposed to explain the origin of reactivity.

  该ñ，ñ “二氧化物-铜（I）配合物已发展到催化将硝基甲烷来ñ甲苯磺酰亚胺。氮杂-亨利反应平稳进行，以高收率和高对映选择性提供相应的硝基胺。建议使用催化循环来解释反应性的起源。