2-(4-Fluorophenyl)cyclohexane-1,3-dione | 459174-25-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-(4-Fluorophenyl)cyclohexane-1,3-dione
• 英文别名: 2-(4-fluorophenyl)-3-hydroxycyclohex-2-en-1-one；4'-fluoro-6-hydroxy-4,5-dihydro-[1,1'-biphenyl]-2(3H)-one
• CAS: 459174-25-5
• 化学式: C₁₂H₁₁FO₂
• 分子量: 206.217
• InChiKey: TWHIFYCIMTVLIM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(4-Fluorophenyl)cyclohexane-1,3-dione 在 三乙胺 、 异丙醇 作用下， 以 乙醇 、 二氯甲烷 、 氯仿 为溶剂， 反应 120.0h， 生成 4a-(4-fluorophenyl)-5-oxo-2-(2-oxo-2-phenylethyl)octahydro-8aH-chromene-8a-carbonitrile
  参考文献：
  名称：

  对映和非对映选择性的连续四取代手性碳在有机催化氧杂萘合成中的应用。

  摘要：

  已开发了涉及1,3-环己二酮的烯酮的有机催化对映和非对映选择性环醚化反应，涉及手性氰醇的原位生成。这种转变为在稠环系统桥头处含有连续四取代手性碳的奥沙德林衍生物提供了第一种催化不对称方法。根据取代基的不同，合成的顺式和反式十氢化萘型支架均具有良好的立体选择性，以及在反式-oxadecalin衍生物的手性季碳部分上积累的一系列官能团。

  DOI：

  10.1021/acs.orglett.0c01501
• 作为产物：
  描述：

  1-氯-4-氟苯 、 1,3-环己二酮 在 potassium phosphate 、 palladium diacetate 、 2-(二叔丁基膦)联苯 作用下， 以 1,4-二氧六环 为溶剂， 反应 12.0h， 以75%的产率得到2-(4-Fluorophenyl)cyclohexane-1,3-dione
  参考文献：
  名称：

  1,2,3-三取代的环戊烷和环己烷作为p物质拮抗剂的关键成分的不对称合成。

  摘要：

  描述了1,2,3-三取代的环戊烷和环己烷的有效不对称合成。开发了三种方法来制备2,3-二取代的环戊烯酮和环己烯酮，这是关键的非手性构建单元。这些中间体可以用（R）-2-甲基恶唑硼烷催化还原，产率高（82-98％）和优良的ee（89-6％）。使用Red-Al直接还原手性烯丙基醇只能得到1,2-抗立体化学（> 99：1）。酯中心的差向异构化，然后进行皂化/结晶，以良好的收率（65-70％）和高的对映体过量（＞ 99％）提供所需的羟基酸。

  DOI：

  10.1021/jo025883m

文献信息

• Catalytic 1,4-Rhodium(III) Migration Enables 1,3-Enynes to Function as One-Carbon Oxidative Annulation Partners in CH Functionalizations
  作者：David J. Burns、Hon Wai Lam

  DOI：10.1002/anie.201406072

  日期：2014.9.8

  1,3‐Enynes containing allylic hydrogens cis to the alkyne are shown to act as one‐carbon partners, rather than two‐carbon partners, in various rhodium‐catalyzed oxidative annulations. The mechanism of these unexpected transformations is proposed to occur through double CH activation, involving a hitherto rare example of the 1,4‐migration of a RhIII species. This phenomenon is general across a variety

  在各种铑催化的氧化成环反应中，含有与炔顺式烯丙基氢的 1,3-烯炔被证明可充当单碳伙伴，而不是双碳伙伴。这些意想不到的转变的机制被认为是通过双C - H激活而发生的，涉及迄今为止罕见的Rh III物种的1,4-迁移例子。这种现象在各种底物中普遍存在，并提供了多种杂环产物。
• The Mechanism of 1,4 Alkyl Group Migration in Hypervalent Halonium Ylides: The Stereochemical Course
  作者：Robert M. Moriarty、Sachin Tyagi、Daniela Ivanov、Mircea Constantinescu

  DOI：10.1021/ja802735f

  日期：2008.6.18

  Rhodium(II)-acetate-catalyzed decomposition of either 1,3-cyclohexanedione phenyliodonium ylide or 5,5-dimethyl-1,3-cyclohexanedione phenyliodonium ylide in the presence of alkyl halides yields the corresponding 3-alkoxy-2-halocyclohex-2-enones via a 1,4 alkyl group migration shown to be concerted and intramolecular. In the case of (S)-alpha-phenethyl chloride, the rearrangement proceeds with essentially

  在烷基卤化物存在下，1,3-环己二酮苯基碘鎓叶立德或 5,5-二甲基-1,3-环己二酮苯基碘鎓叶立德的铑 (II)-乙酸酯催化分解产生相应的 3-烷氧基-2-卤代环己-2 -烯酮通过 1,4 烷基迁移显示是协同和分子内的。在 (S)-α-苯乙基氯的情况下，重排进行时基本上保留了 88.6% 的构型。B3LYP/6-31G 水平的理论计算表明该过程的活化能为 5.4 kcal/mol。在使用烯丙基卤化物，例如二甲基烯丙基或甲基烯丙基氯的情况下，会发生类克莱森重排。为这些过程提出的机械途径包括将烷基卤化物或烯丙基卤化物的卤原子加成到来自碘鎓叶立德的类铑卡宾，以产生经历卤素到氧基团迁移的卤鎓中间体。芳基卤化物，如氯苯、溴苯、碘苯和氟苯，在相同的反应条件下表现不同，产生亲电芳香取代的产物，即2-（4-卤代苯基）1,3-环己二酮。
• Redox-Neutral Ruthenium(II)-Catalyzed Enol-Directed Arene C–H Alkylation with Maleimides
  作者：Sudeshna Mondal、Ratnadeep Bera、Deepan Chowdhury、Suman Dana、Mahiuddin Baidya

  DOI：10.1021/acs.orglett.2c03858

  日期：2023.1.13

  developed under redox-neutral ruthenium(II) catalysis, offering a wide variety of valuable 3-aryl succinimides including amino acid embedded frameworks in good to excellent yields. The products were also aromatized to produce synthetically useful resorcinol-based biaryls. Mechanistic studies support an organometallic pathway with a reversible C–H metalation step for this reaction.

  在氧化还原中性钌 (II) 催化下开发了一种烯醇辅助的区域选择性芳烃 C-H 与马来酰亚胺的烷基化反应，提供了多种有价值的 3-芳基琥珀酰亚胺，包括氨基酸嵌入框架，收率良好至极佳。产物也被芳构化以产生合成有用的基于间苯二酚的联芳基化合物。机理研究支持有机金属途径与该反应的可逆 C-H 金属化步骤。
• Synthesis of Benzopyrans by Pd(II)- or Ru(II)-Catalyzed C–H Alkenylation of 2-Aryl-3-hydroxy-2-cyclohexenones
  作者：Suresh Reddy Chidipudi、Martin D. Wieczysty、Imtiaz Khan、Hon Wai Lam

  DOI：10.1021/ol3033835

  日期：2013.2.1

  2-Aryl-3-hydroxy-2-cyclohexenones are shown to be competent substrates for palladium- and ruthenium-catalyzed C-H alkenylation reactions with terminal alkenes, providing, in most cases, benzopyrans.
• Reactions of a Cyclic Rhodium Carbenoid with Aromatic Compounds and Vinyl Ethers
  作者：Michael C. Pirrung、Jiancun Zhang、Karen Lackey、Daniel D. Sternbach、Frank Brown

  DOI：10.1021/jo00112a036

  日期：1995.4

  Further investigation has been made of the reactions between the cyclic diazo compound 2-diazo-1,3-cyclohexanedione and aromatic heterocycles or vinyl ethers, catalyzed by rhodium carboxylates. The extraordinary reactivity of the carbenoid derived from this diazo compound is shown by its ready reaction with solvents such as dichloromethane, dichloroethane, and fluorobenzene. Detailed investigation of its reactions with furans have shown that steric interactions dominate, both in terms of regioselectivity with unsymmetrical substrates and yield. This reaction provides a useful entry to the furo[2,3-b]furan ring system found in a number of naturally-occurring compounds and is formally a 1,3-dipolar cycloaddition. Products of net C-H insertion and with reverse regiochemistry (furo[3,2-b]furan ring system) were also detected. With pyrroles and thiophenes, cycloadducts were seen in a few cases, but were generally the exception; C-H insertion products dominate these reactions. Vinyl ethers proved reliable reactants in providing dipolar cycloadducts. The results of this study have been interpreted in terms of four pathways: an initial cyclopropanation would produce a spirocyclic dicarbonyl system that on heterolytic cleavage of one of the two cyclopropane bonds would give a zwitterion. The partitioning of such a zwitterion between ring closure and proton transfer would define the ratio of C-H insertion and dipolar cycloaddition products. Both thermodynamic and stereoelectronic arguments have been advanced to explain the observations and were supported by calculations.