(R)-4-(1-hydroxy-2-nitroethyl)benzonitrile

• 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: (R)-4-(1-hydroxy-2-nitroethyl)benzonitrile
• 英文别名: (R)-4-(1-hydroxy-2-nitroethyl)benzonirile；4-(1-hydroxy-2-nitroethyl)benzonitrile；(R)-1-(4-cyanophenyl)-2-nitroethanol；(R)-2-nitro-1-(4-cyanophenyl)ethanol；2-nitro-1-(4-cyanophenyl)ethanol；4-[(1R)-1-hydroxy-2-nitroethyl]benzonitrile
• 化学式: C₉H₈N₂O₃
• 分子量: 192.174
• InChiKey: NXGSXZLSMLYJKP-VIFPVBQESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  89.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  硝基甲烷 、 4-氰基苯甲醛 在 (1S,2R)-2-dimethylamino-1,2-diphenylethanol 、 copper(II) acetate monohydrate 作用下， 以 乙醚 为溶剂， 以78%的产率得到(R)-4-(1-hydroxy-2-nitroethyl)benzonitrile
  参考文献：
  名称：

  氨基醇-铜（II）配合物催化的芳香醛的高对映选择性亨利反应

  摘要：

  氨基醇-Cu II 催化剂：已开发出芳香醛与硝基甲烷之间的高度对映选择性的亨利反应。反应是由易于获得且操作简单的氨基醇-铜（II）催化剂催化的（请参见方案）。总共测试了38种底物，并以高收率和出色的对映选择性获得了R构型的产品。

  DOI：

  10.1002/chem.201201565

文献信息

• A new series of bipyridine based chiral organocatalysts for enantioselective Henry reaction
  作者：Veeramanoharan Ashokkumar、Kumaraguru Duraimurugan、Ayyanar Siva

  DOI：10.1039/c6nj01045h

  日期：——

  We report the design and synthesis of a new series of binaphthol based chiral organocatalysts which can act as metal-free organocatalysts in the enantioselective Henry reaction with very good yield and ee.

  我们报道了一类基于联萘酚的新型手性有机催化剂的设计与合成，这些催化剂可以作为无金属有机催化剂在亨利反应中表现出很好的产率和對映选择性。
• Enantioselective catalysts for the Henry reaction: fine-tuning the catalytic components
  作者：Edwin C. Constable、Guoqi Zhang、Catherine E. Housecroft、Markus Neuburger、Silvia Schaffner、Wolf-D. Woggon、Jennifer A. Zampese

  DOI：10.1039/b9nj00243j

  日期：——

  Catalysts for the asymmetric Henry reaction involving 1,6-bis(3-ethoxy-2-hydroxyphenyl)-(3S,4S)-(−)-diphenyl-2,5-diazahexane (H22) and copper salts have been investigated. Conditions for the conversion of 4-nitrobenzaldehyde to 2-nitro-1-(4-nitrophenyl)ethanol by reaction with nitromethane have been optimized (5 mol% H22, 10 mol% CuI, THF, 295 K and 2 hours or 273 K and 12 hours) resulting in 99% yield and 90–92% ee. These catalytic conditions are effective for other aromatic aldehydes containing electron-withdrawing substituents, and for pyridine carbaldehydes; representative aliphatic aldehydes were converted to the respective β-hydroxynitro derivatives with good enantioselectivities, and in moderate yields. These catalytic conditions were found to be ineffective for simple aromatic aldehydes or those containing electron-releasing substituents.

  关于1,6-双(3-乙氧基-2-羟基苯基)-(3S,4S)-(-)-二苯基-2,5-二氮杂己烷（H22）和铜盐在对称亨利反应中的催化剂研究已经有了进展。通过优化反应条件（5 mol% H22，10 mol% CuI，四氢呋喃，295 K和2小时或273 K和12小时），将4-硝基苯甲醛与硝基甲烷反应转化为2-硝基-1-(4-硝基苯基)乙醇，产率达到了99%，对映体过量率为90-92%。这些催化条件对其他含有吸电子取代基的芳香醛以及吡啶醛同样有效；具有代表性的脂肪醛被转化为相应的β-羟基硝基衍生物，具有良好的对映选择性和适中的产率。这些催化条件对于简单的芳香醛或含有供电子取代基的芳香醛则无效。
• Henry reaction catalyzed by new series of imidazolidine-4-one Cu-complexes
  作者：Pavel Drabina、Eva Horáková、Zdeňka Růžičková、Miloš Sedlák

  DOI：10.1016/j.tetasy.2015.01.001

  日期：2015.2

  Henry reaction of various aldehydes with nitromethane. It was found that these compounds were effective catalysts for this reaction, with enantiomeric excesses being as high as 97%. The enantioselectivities of individual derivatives were different and depended on the substituents attached to stereogenic centers and the configuration of imidazolidine-4-one cycle. High enantiomeric excesses were obtained

  一系列5-叔丁基-2-（吡啶-2-基）咪唑烷-4-酮已经制备和它们的铜（II）配合物研究作为与硝基甲烷各种醛的不对称Henry反应对映选择性催化剂。发现这些化合物是该反应的有效催化剂，对映体过量高达97％。各个衍生物的对映选择性是不同的，取决于对立体异构中心连接的取代基和咪唑烷-4-一环的构型。被不论使用的溶剂的得到高对映体过量。被选为最有效的衍生物在制备用于沙美特罗医用药物，得到对映体过量92％的关键中间体。
• Cu-catalyzed asymmetric Henry reaction promoted by chiral camphor Schiff bases
  作者：Tangqian Jiao、Jingxuan Tu、Gaoqiang Li、Feng Xu

  DOI：10.1016/j.molcata.2016.02.004

  日期：2016.5

  Abstract Five novel chiral camphor Schiff bases have been synthesized and utilized as ligands in asymmetric Henry reaction between nitromethane and aldehydes. The diastereoisomeric Schiff bases 5a and 5a' were separated successfully and gave completely different absolute configurations in the reaction. The reactions were carried out with CuCl-Schiff base 5a complex under mild condition with good yields

  摘要 合成了五种新型手性樟脑席夫碱，并将其用作硝基甲烷与醛的不对称亨利反应的配体。非对映体席夫碱5a和5a'被成功分离，反应中的绝对构型完全不同。该反应在温和条件下用 CuCl-席夫碱 5a 络合物进行，具有良好的收率和对映选择性。这是樟脑衍生的席夫碱首次在不对称亨利反应中用作配体。
• Enantioselective Nitroaldol Reaction Catalyzed by Sterically Modified Salen−Chromium Complexes
  作者：Rafał Kowalczyk、Piotr Kwiatkowski、Jacek Skarżewski、Janusz Jurczak

  DOI：10.1021/jo802107b

  日期：2009.1.16

  A group of modified (salen)Cr(III)Cl complexes with bulky benzylic substituents in the 3,3′-position of the salicylidene moiety have been successfully applied for the asymmetric nitroaldol reaction. The readily accessible complex bearing 3-phenylpent-3-yl groups (2 mol %) leads to β-nitro alcohols in up to 92% yield and 94% ee.

  一组修饰的（salen）Cr（III）Cl配合物在水杨基部分的3,3'-位具有庞大的苄基取代基，已成功地用于不对称硝基醛醇反应。具有3-苯基戊-3-基（2mol％）的容易获得的络合物导致β-硝基醇的产率高达92％和ee为94％。