(R)-3-(1-methyl-2-oxocyclohexyl)propionitrile | 163877-34-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (R)-3-(1-methyl-2-oxocyclohexyl)propionitrile
• 英文别名: (R)-3-(1-methyl-2-oxocyclohexyl)propanenitrile；3-[(1R)-1-methyl-2-oxocyclohexyl]propanenitrile
• CAS: 163877-34-7
• 化学式: C₁₀H₁₅NO
• 分子量: 165.235
• InChiKey: DBHUNYNZTIQTNL-SNVBAGLBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  40.9
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (R)-3-(1-methyl-2-oxocyclohexyl)propionitrile 在 三氟化硼乙醚 、 氢溴酸 、 氯化铵 、 臭氧 、 锌 作用下， 以 四氢呋喃 、 乙醚 、 乙醇 、 二氯甲烷 、 水 为溶剂， 反应 5.6h， 生成 (5aR,9aR)-3-methoxy-3,5a-dimethyl-4,5,6,7,8,9-hexahydrobenzo[c]dioxepine-9a-carbaldehyde
  参考文献：
  名称：

  Artemisinin tricyclic analogs: Role of a methyl group at C-5a

  摘要：

  New artemisinin tricyclic analogs, bearing a methyl group at C-5a were synthetized through ozonation of vinylsilanes. Presence of such a substituent was detrimental to the antimalarial activity of these trioxanes, thus reinforcing the hypothesis that tight hemin-trioxane complexes are involved in the activation phase of these compounds. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)00390-6
• 作为产物：
  描述：

  在 溶剂黄146 作用下， 以 四氢呋喃 为溶剂， 反应 20.0h， 生成 (R)-3-(1-methyl-2-oxocyclohexyl)propionitrile
  参考文献：
  名称：

  The asymmetric Michael reaction involving chiral imines: Use of acrylonitrile as acceptor and subsequent functionalization of the adducts

  摘要：

  Condensation of chiral imines 1 and acrylonitrile led to adduct (R)-6 with an ee greater than or equal to 95 %. This adduct has then been converted into chiral synthons 9, 11, 12 and 17.

  DOI：

  10.1016/0957-4166(94)80071-5

文献信息

• Enantioselective Synthesis of Quaternary Carbon Stereogenic Centers through the Primary Amine-Catalyzed Michael Addition Reaction of α-Substituted Cyclic Ketones at High Pressure
  作者：Ryo Horinouchi、Kouhei Kamei、Riki Watanabe、Nobushige Hieda、Naoki Tatsumi、Keiji Nakano、Yoshiyasu Ichikawa、Hiyoshizo Kotsuki

  DOI：10.1002/ejoc.201500411

  日期：2015.7

  The enantioselective Michael addition reaction of α-substituted cyclic ketones with acrylates was efficiently promoted by a primary amine chiral catalyst under high-pressure conditions (1.0 GPa) in tetrahydrofuran. This method was highly successful for the construction of an all-carbon-substituted quaternary-carbon stereogenic center at the α-position of cyclic ketones in high enantiomeric excess,

  在四氢呋喃中，在高压条件 (1.0 GPa) 下，伯胺手性催化剂有效地促进了 α-取代环酮与丙烯酸酯的对映选择性迈克尔加成反应。该方法在高对映体过量的环酮α位构建全碳取代季碳立体中心非常成功，可方便地应用于(+)-aspidospermidine的正式合成。
• Construction of Stereogenic α,α-Disubstituted Cycloalkanones via 1° Amine Thiourea Dual Catalysis: Experimental Scope and Computational Analyses
  作者：Jun Yong Kang、Ryne C. Johnston、Kevin M. Snyder、Paul Ha-Yeon Cheong、Rich G. Carter

  DOI：10.1021/acs.joc.6b00280

  日期：2016.5.6

  with a ketone containing pre-existing stereocenters has been demonstrated. Computational analyses of the reaction mechanism are reported. In concert with kinetic isotope effect (KIE) experiments, these computational results provide a detailed understanding of the likely mechanism, including the aspects of the organocatalyst scaffold that are critical for stereoselectivity.

  通过利用双功能1°胺硫脲催化剂体系，对有机催化的不对称Pfau-d'Angelo反应进行了机理探索和扩展的实验讨论。在环状酮部分和α，β-不饱和亲电体上都证明了底物范围的显着宽度。已经证明了使用含有预先存在的立体中心的酮来探索该方法的匹配和不匹配选择性。报告了反应机理的计算分析。与动力学同位素效应（KIE）实验相结合，这些计算结果对可能的机理提供了详细的了解，包括对立体选择性至关重要的有机催化剂支架方面。
• Primary Amine, Thiourea-Based Dual Catalysis Motif for Synthesis of Stereogenic, All-Carbon Quaternary Center-Containing Cycloalkanones
  作者：Jun Yong Kang、Rich G. Carter

  DOI：10.1021/ol301272r

  日期：2012.6.15

  The enantioselective synthesis of alpha,alpha-disubstituted cycloalkanones has been developed using a primary amine, thiourea-based dual catalysis pathway. A range of electrophiles and ring sizes are tolerated under the reaction conditions. A possible catalytic cycle is presented to explain the reactivity.
• The asymmetric Michael reaction involving chiral imines: Use of acrylonitrile as acceptor and subsequent functionalization of the adducts
  作者：Didier Desmaële、Fatima Zouhiri、Jean d'Angelo

  DOI：10.1016/0957-4166(94)80071-5

  日期：1994.9

  Condensation of chiral imines 1 and acrylonitrile led to adduct (R)-6 with an ee greater than or equal to 95 %. This adduct has then been converted into chiral synthons 9, 11, 12 and 17.
• Artemisinin tricyclic analogs: Role of a methyl group at C-5a
  作者：Fatima Zouhiri、Didier Desmaële、Jean d'Angelo、Claude Riche、Fréderick Gay、Liliane Cicéron

  DOI：10.1016/s0040-4039(98)00390-6

  日期：1998.5

  New artemisinin tricyclic analogs, bearing a methyl group at C-5a were synthetized through ozonation of vinylsilanes. Presence of such a substituent was detrimental to the antimalarial activity of these trioxanes, thus reinforcing the hypothesis that tight hemin-trioxane complexes are involved in the activation phase of these compounds. (C) 1998 Elsevier Science Ltd. All rights reserved.