(1S,2R)-2-硝基-1,3-二苯基丙烷-1-醇 | 1040924-07-9

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 直链 1,3-二芳基丙烷
• 中文名称: (1S,2R)-2-硝基-1,3-二苯基丙烷-1-醇
• 英文名称: (1S,2R)-2-nitro-1,3-diphenylpropan-1-ol
• 英文别名: (1S,2R)-2-nitro-1,3-diphenylpropanol；2-nitro-1,3-diphenylpropan-1-ol
• CAS: 1040924-07-9
• 化学式: C₁₅H₁₅NO₃
• 分子量: 257.289
• InChiKey: YZSKVRHQRGFFCF-CABCVRRESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  66
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  Β-硝基苯乙烷 、 苯甲醛 在 copper(II) choride dihydrate 、 (1R,2R,4R)-1,7,7-trimethyl-N-[[(2S)-pyrrolidin-2-yl]methyl]bicyclo[2.2.1]heptan-2-amine 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 15.0h， 生成 (1S,2S)-2-硝基-1,3-二苯基丙烷-1-醇 、 (1S,2R)-2-硝基-1,3-二苯基丙烷-1-醇
  参考文献：
  名称：

  C 1对称手性仲二胺的合成及其在不对称铜（II）催化的亨利（硝基醛）反应中的应用

  摘要：

  的一小库Ç 1个（ -对称的手性二胺L1 - L9）通过冷凝构建外型- （ - ） - bornylamine或（+） - （1小号，2小号，5 - [R）-menthylamine与各种Cbz-保护的氨基酸。其中，配体L1 / CuCl 2 ·2H 2O络合物（2.5 mol％）对多种醛和硝基烷之间的亨利反应显示出出色的催化效率，以高收率（高达98％）提供了预期的产物，具有出色的对映选择性（高达99％）和中度到良好的非对映选择性（直到90:10）。该方法耐空气和湿气，已被用于合成（S）-2-氨基-1-（3,4-二甲氧基苯基）乙醇（9），这是（S）-肾上腺素和（S）的关键中间体）-去甲肾上腺素。基于HRMS和L1 / CuCl 2的X射线衍射分析复杂的情况下，提出了一种过渡状态模型来解释不对称感应的起源。低的催化剂负载量，优异的收率和对映选择性，廉价的铜盐以及温和的反应条件使我们的催化体系实用化。

  DOI：

  10.1021/jo102124d

文献信息

• New Highly Asymmetric Henry Reaction Catalyzed by CuII and aC1-Symmetric Aminopyridine Ligand, and Its Application to the Synthesis of Miconazole
  作者：Gonzalo Blay、Luis R. Domingo、Victor Hernández-Olmos、José R. Pedro

  DOI：10.1002/chem.200800069

  日期：2008.5.19

  A new catalytic asymmetric Henry reaction has been developed that uses a C(1)-symmetric chiral aminopyridine ligand derived from camphor and picolylamine. A variety of aromatic, heteroaromatic, aliphatic, and unsaturated aldehydes react with nitromethane and other nitroalkanes in the presence of DIPEA (1.0 equiv), Cu(OAc)(2)*H(2)O (5 mol %), and an aminopyridine ligand (5 mol %) to give the expected

  已开发出一种新的催化不对称亨利反应，该反应使用衍生自樟脑和甲基吡啶胺的C（1）-对称手性氨基吡啶配体。在DIPEA（1.0当量），Cu（OAc）（2）* H（2）O（5 mol％）和氨基吡啶的存在下，各种芳香族，杂芳香族，脂肪族和不饱和醛与硝基甲烷和其他硝基烷反应配体（5摩尔％），以高收率（高达99％），中等至良好的非对映选择性（高达82:18）和出色的对映选择性（高达98％）提供预期的产物。该反应是耐空气的，并且已经用于抗真菌剂咪康唑的合成中。
• New chiral thiols and C2-symmetrical disulfides of Cinchona alkaloids: ligands for the asymmetric Henry reaction catalyzed by CuII complexes
  作者：Mariola Zielińska-Błajet、Jacek Skarżewski

  DOI：10.1016/j.tetasy.2009.07.020

  日期：2009.9

  Seven Cinchona alkaloids were reacted with thioacetic acid and Bu3P/diethyl diazadicarboxylate in THF at 0-25 degrees C to give the corresponding thiolacetates with complete inversion of configuration at the substitution center. The thus obtained chiral thiolesters were converted into thiols and these compounds were oxidized to the respective disulfides of C-2-symmetry. Both C-9 thioles and disulfides were tested as chiral ligands in the Cu-catalyzed asymmetric Henry reaction. When the thiol derivatives of an 8,9-like configuration were applied in the reaction of benzaldehyde and nitromethane, the obtained nitroaldol was of the same absolute configuration as the catalyst and the observed enantioselectivity was up to 83% ee. These ligands gave higher ees than the corresponding thioethers, disulfides, and thioles of 8,9-unlike configuration. The results obtained are in agreement with the proposed transition-state model involving nucleophilic attack of a deprotonated nitromethane directed preferably at one side of the O-complexed benzaldehyde. (C) 2009 Elsevier Ltd. All rights reserved.
• Asymmetric nitroaldol reaction catalyzed by copper–diamine complexes: selective construction of two contiguous stereogenic centers
  作者：Rafał Kowalczyk、Jacek Skarżewski

  DOI：10.1016/j.tetasy.2009.10.001

  日期：2009.11

  Chiral copper(II) complexes of secondary bisamines derived from 1,2-diaminocyclohexane were successfully used in the diastereoselective nitroaldol reaction. The reactions were carried out in the presence of 10 mol % of the Cu(II) complex and 7.7 mol % of i-Pr2NEt in 2-propanol at -30 degrees C. Good to excellent yields, enantioselectivities of up to 99%, and moderate to excellent diastereoselectivities were obtained for both aromatic or aliphatic aldehydes and various prochiral nitrocompounds forming the corresponding beta-nitroalcohols with two contiguous stereocenters. (C) 2009 Elsevier Ltd. All rights reserved.
• Synthesis of <i>C</i>₁-Symmetric Chiral Secondary Diamines and Their Applications in the Asymmetric Copper(II)-Catalyzed Henry (Nitroaldol) Reactions
  作者：Yirong Zhou、Junfang Dong、Fanglin Zhang、Yuefa Gong

  DOI：10.1021/jo102124d

  日期：2011.1.21

  A small library of C1-symmetric chiral diamines (L1−L9) was constructed via condensing exo-(−)-bornylamine or (+)-(1S,2S,5R)-menthylamine with various Cbz-protected amino acids. Among them, ligand L1/CuCl2·2H2O complex (2.5 mol %) shows outstanding catalytic efficiency for Henry reaction between a variety of aldehydes and nitroalkanes to afford the expected products in high yields (up to 98%) with

  的一小库Ç 1个（ -对称的手性二胺L1 - L9）通过冷凝构建外型- （ - ） - bornylamine或（+） - （1小号，2小号，5 - [R）-menthylamine与各种Cbz-保护的氨基酸。其中，配体L1 / CuCl 2 ·2H 2O络合物（2.5 mol％）对多种醛和硝基烷之间的亨利反应显示出出色的催化效率，以高收率（高达98％）提供了预期的产物，具有出色的对映选择性（高达99％）和中度到良好的非对映选择性（直到90:10）。该方法耐空气和湿气，已被用于合成（S）-2-氨基-1-（3,4-二甲氧基苯基）乙醇（9），这是（S）-肾上腺素和（S）的关键中间体）-去甲肾上腺素。基于HRMS和L1 / CuCl 2的X射线衍射分析复杂的情况下，提出了一种过渡状态模型来解释不对称感应的起源。低的催化剂负载量，优异的收率和对映选择性，廉价的铜盐以及温和的反应条件使我们的催化体系实用化。