2-(1-(4-fluorophenyl)-3-oxo-3-phenylpropyl)malononitrile | 137502-97-7

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物
• 英文名称: 2-(1-(4-fluorophenyl)-3-oxo-3-phenylpropyl)malononitrile
• 英文别名: 2-[1-(4-Fluorophenyl)-3-oxo-3-phenylpropyl]propanedinitrile
• CAS: 137502-97-7
• 化学式: C₁₈H₁₃FN₂O
• 分子量: 292.312
• InChiKey: ZCTYZVLWSCGDSY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  64.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-(1-(4-fluorophenyl)-3-oxo-3-phenylpropyl)malononitrile 在 氢氧化钾 、 selenium 作用下， 以 乙醇 为溶剂， 反应 1.5h， 生成 4-(4-Fluoro-phenyl)-2-methylselanyl-6-phenyl-1,4-dihydro-pyridine-3-carbonitrile
  参考文献：
  名称：

  Sharanin, Yu. A.; Dyachenko, V. D.; Litvinov, V. P., Journal of general chemistry of the USSR, 1991, vol. 61, # 4.2, p. 856 - 861

  摘要：

  DOI：
• 作为产物：
  描述：

  4-fluorochalcone 、 丙二腈 以 neat (no solvent) 为溶剂， 反应 0.75h， 以96%的产率得到2-(1-(4-fluorophenyl)-3-oxo-3-phenylpropyl)malononitrile
  参考文献：
  名称：

  Synergistic effect of ultrasound and deep eutectic solvent choline chloride–urea as versatile catalyst for rapid synthesis of β-functionalized ketonic derivatives

  摘要：

  A green protocol for efficient synthesis of beta-functionalized ketonic derivatives is achieved with the combination of ultrasound and the deep eutectic solvent (DES) choline chloride-urea [ChCl:urea (1:2)]. Under optimized conditions, nucleophilic attack of active methylene on alpha,beta-unsaturated ketones gives the conjugate addition product in the short span of 40-50 min an excellent yield of 89-95%. The experimental procedure is very simple, easy to set up, solvent free and completely eliminates the use of any toxic metal catalyst. The use of ChCl:urea as a biodegradable, recyclable and reusable catalyst (up to five cycles) further increases the scope of the developed methodology. (C) 2014 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molliq.2014.02.016

文献信息

• Highly Enantioselective Kinetic Resolution of Michael Adducts through N-Heterocyclic Carbene Catalysis: An Efficient Asymmetric Route to Cyclohexenes
  作者：Xiang-Yu Chen、Sun Li、Qiang Liu、Mukesh Kumar、Anssi Peuronen、Kari Rissanen、Dieter Enders

  DOI：10.1002/chem.201802420

  日期：2018.7.11

  A highly efficient strategy for the kinetic resolution of Michael adducts was realized using a chiral N‐heterocyclic carbene catalyst. The kinetic resolution provides a new convenient route to single diastereomers of cyclohexenes and Michael adducts in good yields with high enantiomeric excesses (up to 99 % ee with a selectivity factor of up to 458). This “two flies with one swat” concept allows the

  使用手性N-杂环卡宾催化剂实现了迈克尔加合物动力学拆分的高效策略。动力学拆分提供了一条新的便捷途径，可以以高收率和高对映异构体过量（高达99％ee，选择性因子高达458）获得环己烯和迈克尔加合物的单一非对映异构体。这种“两只苍蝇一拍打”的概念允许通过一次转换同时合成这两种具有合成价值的化合物类别。
• Highly enantioselective Michael addition of malononitrile to α,β-unsaturated ketones
  作者：Xuefeng Li、Lingfeng Cun、Chunxia Lian、Ling Zhong、Yingchun Chen、Jian Liao、Jin Zhu、Jingen Deng

  DOI：10.1039/b713129a

  日期：——

  The highly enantioselective Michael addition of malononitrile to acyclic and cyclic alpha,beta-unsaturated ketones has been developed. The Michael reaction catalyzed by a primary amine derived from quinidine proceeded smoothly and provided the desired adducts with excellent enantioselectivities (83-97% ee).

  已经开发出丙二腈向非环状和环状的α，β-不饱和酮的高度对映选择性的迈克尔加成。由奎尼丁衍生的伯胺催化的迈克尔反应进行得很顺利，并为所需的加合物提供了极佳的对映选择性（83-97％ee）。
• Visible-Light-Accelerated Pd-Catalyzed Cascade Addition/Cyclization of Arylboronic Acids to γ- and β-Ketodinitriles for the Construction of 3-Cyanopyridines and 3-Cyanopyrrole Analogues
  作者：Amitava Rakshit、Prashant Kumar、Tipu Alam、Hirendranath Dhara、Bhisma K. Patel

  DOI：10.1021/acs.joc.0c01703

  日期：2020.10.2

  via a Pd-catalyzed coupling of arylboronic acid with 2-(3-oxo-1,3-diarylpropyl)malononitrile and 2-(2-oxo-2-arylethyl)malononitrile, respectively, under mild reaction conditions, followed by intramolecular cyclization of an intermediate formed after the regeneration of the catalyst under acidic reaction conditions. The cascade reactions proceed in 1,2-dichloroethane solvent under visible-light irradiation

  一锅合成策略的2,4,6-三芳基烟腈和2,5-二芳基-1 H-吡咯-3-腈是通过Pd催化的芳基硼酸与2-（3-oxo-1）偶联而完成的，在温和的反应条件下，分别将3-3-二芳基丙基）丙二腈和2-（2-氧代-2-芳基乙基）丙二腈，然后在酸性反应条件下，将催化剂再生后形成的中间体进行分子内环化。级联反应在1,2-二氯乙烷溶剂中在可见光照射下进行，并且在催化量的Pd（OAc）2存在下原位生成活性催化剂和2,2'-联吡啶。活性Pd催化剂借助金属到配体的电荷转移（MLCT）进行光激发，随后芳基硼酸发生氧化还原反金属化，因此无需任何外源光敏剂。以高收率分离出由新的C–C，C–N，C aN和两个新的C═C键组成的目标产物。
• A dynamic kinetic asymmetric transfer hydrogenation–cyclization tandem reaction: an easy access to chiral 3,4-dihydro-2H-pyran-carbonitriles
  作者：Dongsong Zheng、Qiankun Zhao、Xiaoying Hu、Tanyu Cheng、Guohua Liu、Wei Wang

  DOI：10.1039/c7cc02156a

  日期：——

  (mesitylene)RuCl(monosulfonated diamine) catalysed dynamic kinetic resolution (DKR)–asymmetric transfer hydrogenation (ATH) process is developed for highly enantio- (up to 99% ee) and diastereo- (up to 98:2 dr) selective reduction of challenging racemic α-aryl-γ-keto malononitriles. A spontaneous cyclization reaction of the hydrogenation products delivers a cascade process for efficient synthesis of useful enantioenriched

  开发了一种手性（间苯三甲）RuCl（单磺化二胺）催化的动态动力学拆分（DKR）-不对称转移氢化（ATH）工艺，用于高度对映体（高达99％ee）和非对映体（高达98 ：2 dr）的选择性降低具有挑战性的外消旋α-芳基-γ-酮基丙二腈。氢化产物的自发环化反应提供了一种级联过程，用于有效合成有用的对映体富集的3,4-二氢-2 H-吡喃-腈。
• Visible/solar-light-driven thiyl-radical-triggered synthesis of multi-substituted pyridines
  作者：Ashish Kumar Sahoo、Amitava Rakshit、Avishek Pan、Hirendra Nath Dhara、Bhisma K. Patel

  DOI：10.1039/d3ob00009e

  日期：——

  light-triggered synthesis of thio-functionalized pyridines is demonstrated using γ-ketodinitriles, thiols, and eosin Y as the photocatalyst. The reaction proceeds via the selective attack on one of the cyano groups by an in situ generated thiyl radical. The reaction also proceeds with nearly equal efficiency using direct sunlight. Large-scale synthesis and a few useful synthetic transformations of the substituted

  使用 γ-酮二腈、硫醇和曙红 Y 作为光催化剂，证明了光触发合成硫代功能化吡啶。反应通过原位生成的硫自由基选择性攻击其中一个氰基进行。利用直射阳光，反应也能以几乎相同的效率进行。还进行了取代吡啶的大规模合成和一些有用的合成转化。