环己酮,3-(1-甲基-1-硝基乙基)-,(3R)- | 160632-29-1

• 分子结构分类: 有机化合物 - 有机1,3-偶极化合物 - 烯丙基型1,3-偶极有机化合物
• 中文名称: 环己酮,3-(1-甲基-1-硝基乙基)-,(3R)-
• 英文名称: (R)-3-(2-nitropropan-2-yl)cyclohexanone
• 英文别名: (3R)-3-(2-nitropropan-2-yl)cyclohexan-1-one
• CAS: 160632-29-1
• 化学式: C₉H₁₅NO₃
• 分子量: 185.223
• InChiKey: AQRSKQXZONHAFO-SSDOTTSWSA-N

物化性质

• 熔点：
  61-63 °C
• 沸点：
  302.1±15.0 °C(Predicted)
• 密度：
  1.119±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  62.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2R,3R)-(-)-2,3-丁二醇 、 环己酮,3-(1-甲基-1-硝基乙基)-,(3R)- 生成 (2R,3R,7R)-2,3-Dimethyl-7-(1-methyl-1-nitro-ethyl)-1,4-dioxa-spiro[4.5]decane
  参考文献：
  名称：

  4-trans-Amino-proline based di- and tetrapeptides as organic catalysts for asymmetric C–C bond formation reactions

  摘要：

  4-trans-Amino-proline based di- and tetrapeptides have been successfully applied as chiral organocatalysts in the enantioselective conjugate addition of nitroalkanes to cyclic enones and the direct aldol reaction. Two 4-trans-amino-proline residues were shown to be sufficient enough to catalyze the conjugate addition reactions with up to 88% ee and up to 100% yield. It has been demonstrated that 4-trans-amino-proline based di- and tetrapeptides are significantly more active than L-proline (at 30 mol %) and can catalyze the direct aldol reaction with good yield and enantioselectivity within 3 h and at lower catalyst loading (5 mol %). (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2006.03.012
• 作为产物：
  描述：

  2-环己烯-1-酮 、 2-硝基丙烷 在 N-[(1R,2R)-2-氨基环己基]-N'-[3,5-双(三氟甲基)苯基]硫脲 作用下， 以87%的产率得到环己酮,3-(1-甲基-1-硝基乙基)-,(3R)-
  参考文献：
  名称：

  通过硝基链烷烃向环β-取代的α，β-烯酮的有机催化不对称共轭加成反应，对带有季碳立体中心的功能化环酮的多功能研究

  摘要：

  已经开发了一种通用的有机催化不对称共轭硝基链烷烃加成到β-取代的环状α，β-烯酮上的环状酮，其在β-C处带有全碳四元立体异构中心。这是我们在（-）-haliclonin A的全合成过程中开发的方法的扩展，该方法的特点是采用结构相对简单，廉价且易于获得的伯胺-硫脲衍生自（R，R）-1,2-二氨基环己烷为手性催化剂。该方法显示了广泛的底物范围，良好的官能团耐受性，可快速获得多功能手性化合物。该方法的合成潜力通过将硝基酮加合物一步转化为其他四类化合物来证明。通过将手性HPLC分析的保留时间和比旋光度与已知化合物的保留时间进行比较，可以确定加合物的绝对构型。根据DFT计算研究，合理选择了对映选择性控制机制。

  DOI：

  10.1016/j.tet.2021.132005

文献信息

• Catalytic asymmetric Michael addition of nitroalkane to enone and enal
  作者：Masahiko Yamaguchi、Tai Shiraishi、Yoshihiro Igarashi、Masahiro Hirama

  DOI：10.1016/0040-4039(94)88290-8

  日期：1994.10

  L-Proline rubidium salt catalyzes the asymmetric Michael addition of nitroalkanes to enones and an enal. (R)-Adducts were obtained from cyclic (Z)-enones and (S)-adducts from acyclic (E)-enones. Bu3SnH treatment of the products replaced the nitro group with hydrogen atom. The overall transformation allows the asymmetric alkylation of enones at the β-carbon atom.

  L-脯氨酸rub盐催化硝基烷烃向烯酮和烯醛的不对称迈克尔加成反应。从环状（Z）-烯酮获得（R）-加合物，从无环（E）-烯酮获得（S）-加合物。Bu 3 SnH处理的产物用氢原子取代了硝基。整体转化允许β-碳原子上烯酮的不对称烷基化。
• Synthesis and evaluation of guanidinyl pyrrolidines as bifunctional catalysts for enantioselective conjugate additions to cyclic enones
  作者：Sunil V. Pansare、Rajinikanth Lingampally

  DOI：10.1039/b812038b

  日期：——

  Guanidinyl pyrrolidines derived from ‘S’-proline are effective catalysts for the enantioselective conjugate addition of malonate, nitroalkane and other carbon and heteroatom nucleophiles to cyclohexenone and cyclopentenone in the absence of basic additives. The stereoselectivity is strongly dependant on catalyst loading as well as reaction concentration.

  衍生自“ S ”-脯氨酸的胍基吡咯烷是将丙二酸酯，硝基烷和其他碳原子和杂原子亲核试剂对映选择性共轭加成的有效催化剂。环己烯酮 和 环戊烯酮在没有碱性添加剂的情况下。立体选择性很大程度上取决于催化剂的负载以及反应浓度。
• Catalytic Asymmetric Conjugate Addition of Nitroalkanes to Cycloalkenones
  作者：Stephen Hanessian、Vinh Pham

  DOI：10.1021/ol000170g

  日期：2000.9.1

  Nitroalkanes add to cyclic and acyclic enones in an enantioselective manner in the presence of catalytic quantities of L-proline and trans-2,5-dimethylpiperazine as excess additive.

  在催化量的L-脯氨酸和反式2,5-二甲基哌嗪作为过量添加剂存在下，硝基烷以对映选择性的方式添加到环状和无环烯酮中。
• Trends in Asymmetric Michael Reactions Catalysed by Tripeptides in Combination with an Achiral Additive in Different Solvents
  作者：Svetlana B. Tsogoeva、Sunil B. Jagtap、Zoya A. Ardemasova、Victor N. Kalikhevich

  DOI：10.1002/ejoc.200400243

  日期：2004.10

  as chiral catalysts for asymmetric Michael addition reactions in the presence of an achiral additive has been tested in different solvents (CHCl3, acetone, DMF, DMSO and the room-temperature ionic liquid [bmim]PF6). The dependence of yields and enantiomeric excesses on the solvent used has been demonstrated. The experiments show that the combination of additive and peptides provides a catalytic system

  在不同溶剂（CHCl3、丙酮、DMF、DMSO 和室温离子液体 [bmim]PF6）中测试了三肽 3、6 和 12 作为手性催化剂在非手性添加剂存在下进行不对称迈克尔加成反应的潜力. 已经证明了收率和对映体过量对所用溶剂的依赖性。实验表明，添加剂和肽的组合提供了一个似乎比其各部分总和更好的催化系统。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
• A versatile organocatalyst for the asymmetric conjugate addition of nitroalkanes to enones
  作者：Claire E. T. Mitchell、Stacey E. Brenner、Steven V. Ley

  DOI：10.1039/b511441a

  日期：——

  5-Pyrrolidin-2-yltetrazole performs as an improved catalyst for the asymmetric addition of a range of nitroalkanes to cyclic and acyclic enones, with good to excellent enantioselectivity.

  5-吡咯烷基-2-基四唑用作改进的催化剂，用于将一系列硝基烷烃不对称地加成至环状和非环状烯酮中，具有良好至优异的对映选择性。