(S)-2-((R)-1-(4-cyano-phenyl)-2-nitro-ethyl)-cyclohexanone

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (S)-2-((R)-1-(4-cyano-phenyl)-2-nitro-ethyl)-cyclohexanone
• 英文别名: 4-[(1R)-2-nitro-1-[(2S)-2-oxocyclohexyl]ethyl]benzonitrile；4-[(1R)-2-nitro-1-[(1S)-2-oxocyclohexyl]ethyl]benzonitrile
• 化学式: C₁₅H₁₆N₂O₃
• 分子量: 272.304
• InChiKey: CTZBRUNXOXMLOI-KBPBESRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  86.7
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  4-(2-硝基乙烯基)苯甲腈 、 环己酮 在 polystyrene supported (S)-1-benzoyl-3-(pyrrolidine-2-yl)thiourea 作用下， 以 neat (no solvent) 为溶剂， 反应 48.0h， 以99%的产率得到(S)-2-((R)-1-(4-cyano-phenyl)-2-nitro-ethyl)-cyclohexanone
  参考文献：
  名称：

  Polystyrene supported benzoylthiourea—pyrrolidine organocatalyst for the enantioselective Michael addition

  摘要：

  Herein the preparation of a swellable pearl-like copolymer of styrene with anchored (S)-1-benzoyl-3-(pyrrolidine-2-ylmethyl)thiourea (20-600 mu m) and its application as a recyclable organocatalyst for the Michael addition of ketones to functionalized beta-nitrostyrenes is described. The rate of the reaction taking place in the matrix of the swellable polymeric catalyst was comparable with the reaction rate in homogeneous medium. The corresponding functionalized 4-nitroketones were formed quantitatively with the enantiomeric excesses up to 98% ee. After a fivefold recycling of the catalyst, no decrease in the yield was detected, but the enantioselectivity was slightly lowered (95 -> 88% ee). (C) 2016 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2016.06.015

文献信息

• l-Proline derived triamine as a highly stereoselective organocatalyst for asymmetric Michael addition of cyclohexanone to nitroolefins
  作者：Haibin Chen、Yu Wang、Siyu Wei、Jian Sun

  DOI：10.1016/j.tetasy.2007.05.035

  日期：2007.6

  triamine 4 has been developed as a highly efficient and stereoselective organocatalyst for the asymmetric Michael addition of cyclohexanone to nitroolefins. In the presence of (CF3SO2)2NH, 4 catalyzed the reaction of cyclohexanone to a variety of nitroolefins with high yields (up to 99%) and excellent diastereoselectivities (up to 99:1 dr) and enantioselectivities (up to 98% ee).

  脯氨酸衍生的三胺4已被开发为一种高效且立体选择性的有机催化剂，用于环己酮向硝基烯烃的不对称迈克尔加成反应。在（CF 3 SO 2）2 NH存在下，4催化环己酮与各种硝基烯烃的反应，产率高（高达99％），非对映选择性（高达99：1 dr）和对映选择性（高达98）。 ％ee）。
• Highly Efficient Amine Organocatalysts Based on Bispidine for the Asymmetric Michael Addition of Ketones to Nitroolefins
  作者：Zhigang Yang、Jie Liu、Xiaohua Liu、Zhen Wang、Xiaoming Feng、Zhishan Su、Changwei Hu

  DOI：10.1002/adsc.200800341

  日期：2008.9.5

  highly diastereoselective and enantioselective Michael addition of cyclohexanone, acetone and other ketones to nitroolefins was developed by the use of an amine organocatalyst based on bispidine. Additionally, a theoretical study of transition structures revealed that this bispidine-based primary-secondary amine catalyst could serve through an enamine intermediate and H-bond interaction, which was

  通过使用基于联吡啶的胺有机催化剂，开发了环己酮，丙酮和其他酮向硝基烯烃的高度非对映选择性和对映选择性迈克尔加成反应。另外，对过渡结构的理论研究表明，这种基于联吡啶的伯-仲胺催化剂可以通过烯胺中间体和氢键相互作用而起作用，这对于该反应的反应性和选择性很重要。
• Polymer-Immobilized Pyrrolidine-Based Chiral Ionic Liquids as Recyclable Organocatalysts for Asymmetric Michael Additions to Nitrostyrenes under Solvent-Free Reaction Conditions
  作者：Pinhua Li、Lei Wang、Min Wang、Yicheng Zhang

  DOI：10.1002/ejoc.200701037

  日期：2008.3

  immobilized pyrrolidine-based chiral ionic liquid 5a was synthesized and was found to be a highly efficient catalyst for the Michael additions of ketones and aldehydes to nitrostyrenes, which afforded the corresponding adducts in good yields (up to 97 %), excellent enantioselectivities (up to >99 % ee) and high diastereoselectivities (up to >99:1 dr) under solvent-free reaction conditions. In addition, the

  合成了聚合物固定化吡咯烷基手性离子液体 5a，发现它是酮和醛与硝基苯乙烯迈克尔加成反应的高效催化剂，以良好的收率（高达 97%）提供相应的加合物，优异的对映选择性（在无溶剂反应条件下高达 >99 % ee）和高非对映选择性（高达 >99:1 dr）。此外，催化剂 5a 可以重复使用至少八次，而不会显着降低其催化活性和立体选择性。 (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
• Highly Enantioselective Water-Compatible Organocatalyst for Michael Reaction of Ketones to Nitroolefins
  作者：Vishnumaya、Vinod K. Singh

  DOI：10.1021/ol070082x

  日期：2007.3.1

  A chiral diamine was found to catalyze enantioselective addition of ketones to nitroolefins in aqueous/saline/organic media. The products were obtained with excellent diastereoselectivities (syn/anti = 99:1) and enantioselectivities up to 99%. The reaction could be facilitated using a mild acid. [reaction: see text]

  发现手性二胺可在水/盐/有机介质中催化酮向硝基烯烃的对映选择性加成。获得的产物具有优异的非对映选择性（syn / anti = 99：1），对映选择性高达99％。使用弱酸可以促进反应。[反应：看文字]
• Dichloro[TADDOLato(2−)‐ <i>O</i> , <i>O</i> ′]titanium/Dichlorobis[1‐methylethoxy]titanium‐Mediated, Highly Diastereo‐ and Enantioselective Additions of Silyl Enol Ethers to Nitro Olefins and [3+2] Cycloadditions of Primary Adducts to Acetylenes
  作者：Dieter Seebach、Ilya M. Lyapkalo、Robert Dahinden

  DOI：10.1002/(sici)1522-2675(19991110)82:11<1829::aid-hlca1829>3.0.co;2-#

  日期：1999.11.10

  The diastereoselective, Ti-Lewis-acid-mediated, low-temperature addition of silyl enol ethers to 1-aryl-2-nitroethenes (Scheme 1) occurs enantioselectively with dichloro[TADDOLato(2-)-O,O']titanium 3 (TADDOL = alpha,alpha,alpha',alpha'-tetraaryl-1,3-dioxolane-4,5-dimethanol) (Scheme 2). At least 3 equiv. of Lewis acid are required for high conversions (yields). However, the chiral Lewis acid 3 can be 'diluted' with the achiral Cl2Ti(OCHMe2)(2) analog (ratio 1:2.5), with hardly any loss of enantioselectivity! Both, the primary (4 + 2) cycloadducts(B, 9) and the gamma-nitro ketones (A, la-h, 5, 7),formed by hydrolysis, can be isolated in good yields and with high configurational purities (Schemes 3 and 4, and Table 1). The relative and absolute configurations (2S,1'R) of the products 1 from cyclohexanone silyl enol ether and 1-aryl(including 1-heteroaryl)-2-nitroethenes (obtained with (R,R)-TADDOLate) are assigned by NMR spectroscopy, and optical comparison and correlation with literature data, as well as by anomalous-dispersion X-ray crystal-structure determination (nitro ketone Ic: I;ig.). The nitro ketone 7 from cyclohex-2-enone and 4-methoxy-beta-nitrostyrene was cyclized (via a silyl nitronate C; Scheme 5) to the nitroso acetal 8, and one of the bicyclic nitronate primary adducts 9 underwent a [3 + 2] cycloaddition to phenylacetylene and to ethyl 2-butynoate to give, after a ring-contracting rearrangement, tricyclic aziridine derivatives with five consecutive stereocenters (10, 11; Scheme 5 and Table 2), in enantiomerically pure form. With an aliphatic nitro olefin. the Ti-TADDOLate-mediated reaction with (silyloxy)cyclohexene led to a moderate yield, but the product 4 was isolated in a high configurational purity.