3-(1-nitro-propyl)-cyclohexanone | 914398-46-2

• 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
• 英文名称: 3-(1-nitro-propyl)-cyclohexanone
• 英文别名: (1'S,3R)-3-(1'-nitropropyl)cyclohexanone；(+)-(R)-3-((S)-1-nitropropyl)cyclohexan-1-one；(3R)-[(1S-nitropropyl)]cyclohexanone；(3R)-3-[(1S)-1-nitropropyl]cyclohexan-1-one
• CAS: 914398-46-2
• 化学式: C₉H₁₅NO₃
• 分子量: 185.223
• InChiKey: DCMXSTJIUDEKDG-APPZFPTMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  13
• 可旋转键数：
  2
• 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：

  3-(1-nitro-propyl)-cyclohexanone 、 (2R,3R)-(-)-2,3-丁二醇 在 对甲苯磺酸 作用下， 以 苯 为溶剂， 反应 1.0h， 生成 (2R,3R,7R)-2,3-Dimethyl-7-((S)-1-nitro-propyl)-1,4-dioxa-spiro[4.5]decane 、 (2R,3R,7R)-2,3-Dimethyl-7-((R)-1-nitro-propyl)-1,4-dioxa-spiro[4.5]decane
  参考文献：
  名称：

  Optimization of the Catalytic Asymmetric Addition of Nitroalkanes to Cyclic Enones with trans-4,5-Methano-l-proline

  摘要：

  The conjugate addition of symmetrical 2-nitroalkanes to 2-cycloalkenones catalyzed by trans-4,5-methano-L-proline proceeds with > 99% ee and excellent chemical yields. 1-Nitroalkanes afford diastereomeric syn/anti products that can be separated with good individual enantioselectivities. Proline hydroxamic acid and its trans-4,5-methano-L-proline hydroxamic acid are also effective organocatalysts in the addition of 2-nitropropane to 2-cyclohexenone (75% and 81% ee, respectively).

  DOI：

  10.1021/ol0618407
• 作为产物：
  描述：

  2-环己烯-1-酮 在 盐酸 、 (R,R)-N-spiro C₂-symmetric quaternary ammonium bifluoride 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 3.0h， 生成 3-(1-nitro-propyl)-cyclohexanone
  参考文献：
  名称：

  手性四氟化铵季铵盐催化的环状α，β-不饱和酮的不饱和迈克尔硅酸酯的不对称迈克尔加成反应：旋光性γ-硝基酮的烯醇甲硅烷基醚的分离和选择性官能化

  摘要：

  通过将N-螺碳C 2对称的手性四氟化季铵盐1作为有效催化剂，实现了对环α，β-不饱和酮的高对映选择性迈克尔加成反应，为光学上制备烯醇式甲硅烷基醚提供了一条新途径。活性γ-硝基酮。通过光学活性的烯醇甲硅烷基醚的非对映选择性衍生化为具有三个连续的立体化学定义的立体中心的相应的α-取代的环酮，已经证明了该转化的合成效用。

  DOI：

  10.1016/j.tetlet.2005.10.154

文献信息

• A versatile approach to functionalized cyclic ketones bearing quaternary carbon stereocenters via organocatalytic asymmetric conjugate addition of nitroalkanes to cyclic β-substituted α,β-Enones
  作者：Si-Jia Yu、Ya-Nan Zhu、Jian-Liang Ye、Pei-Qiang Huang

  DOI：10.1016/j.tet.2021.132005

  日期：2021.3

  quaternary stereogenic centers at β-C has been developed. This is an extension of the method that we developed during the total synthesis of (−)-haliclonin A, which features the employment of structurally relatively simple, cheap and easily available primary amine-thiourea derived from (R,R)-1,2-diaminocyclohexane as the chiral catalyst. The method shows wide substrate scope, good functional group tolerance

  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。
• <i>N</i>-Spiro Chiral Quaternary Ammonium Bromide Catalyzed Diastereo- and Enantioselective Conjugate Addition of Nitroalkanes to Cyclic α,β-Unsaturated Ketones under Phase-Transfer Conditions
  作者：Takashi Ooi、Saki Takada、Shingo Fujioka、Keiji Maruoka

  DOI：10.1021/ol0517170

  日期：2005.11.1

  [reaction, structure: see text] Conjugate addition of various prochiral nitroalkanes to cyclic alpha,beta-unsaturated ketones was found to be efficiently catalyzed by N-spiro C2-symmetric chiral quaternary ammonium bromide 1b possessing a 3,5-bis(3,4,5-trifluorophenyl)phenyl substituent under solid-liquid phase-transfer conditions to afford the corresponding gamma-nitro ketones in excellent chemical yields

  [反应，结构：见正文]已发现，具有3,5-bis（3,3,3-在固-液相转移条件下的4,5-三氟苯基）苯基取代基以优异的化学收率得到前所未有的非对映和对映体控制水平，从而提供相应的γ-硝基酮。
• Asymmetric conjugate addition of nitroalkanes to enones with a chiral α-aminophosphonate catalyst
  作者：Marcus Malmgren、Johan Granander、Mohamed Amedjkouh

  DOI：10.1016/j.tetasy.2008.07.007

  日期：2008.8

  Chiral diethyl (2R)-tetrahydropyrro-2-ylphosphonate is an effective catalyst for the Michael addition of nitroalkanes to alpha,beta-unsaturated ketones. This Study revealed that the hydrate salt of this alpha-aminophosphonate was found to be a better catalytic species. Moderate to high enantioselectivities were achieved in reactions that tolerate various nitroalkanes and enones in the presence of low loading of both catalyst ( 10 mol %) and bulk base (25 mol %). (C) 2008 Published by Elsevier Ltd.
• Substrate-Controlled and Organocatalytic Asymmetric Synthesis of Carbocyclic Amino Acid Dipeptide Mimetics
  作者：Stephen Hanessian、Dilip K. Maji、Subramaniyan Govindan、Riccardo Matera、Marina Tintelnot-Blomley

  DOI：10.1021/jo100017t

  日期：2010.5.7

  The asymmetric synthesis of a carbocyclic delta-amino acid representing the P-2/P-3 subunit of a nonpeptidic truncated peptidomimetic molecule is described relying on two independent approaches.
• Optimization of the Catalytic Asymmetric Addition of Nitroalkanes to Cyclic Enones with <i>trans</i>-4,5-Methano-<scp>l</scp>-proline
  作者：Stephen Hanessian、Zhihui Shao、Jayakumar S. Warrier

  DOI：10.1021/ol0618407

  日期：2006.10.1

  The conjugate addition of symmetrical 2-nitroalkanes to 2-cycloalkenones catalyzed by trans-4,5-methano-L-proline proceeds with > 99% ee and excellent chemical yields. 1-Nitroalkanes afford diastereomeric syn/anti products that can be separated with good individual enantioselectivities. Proline hydroxamic acid and its trans-4,5-methano-L-proline hydroxamic acid are also effective organocatalysts in the addition of 2-nitropropane to 2-cyclohexenone (75% and 81% ee, respectively).