1,5-bis(4-fluorophenyl)penta-1,4-diyn-3-ol | 1430234-79-9

• 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: 1,5-bis(4-fluorophenyl)penta-1,4-diyn-3-ol
• 英文别名: 1,5-Bis(4-fluorophenyl)penta-1,4-diyn-3-ol
• CAS: 1430234-79-9
• 化学式: C₁₇H₁₀F₂O
• 分子量: 268.263
• InChiKey: GCNWPVWAMRIWDH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1,5-bis(4-fluorophenyl)penta-1,4-diyn-3-ol 在 manganese(IV) oxide 、 1,1'-双(二苯基膦)二茂铁 、 chloro(1,5-cyclooctadiene)rhodium(I) dimer 、 氯苯 作用下， 以 二氯甲烷 为溶剂， 反应 25.5h， 生成 1-氟-4-[4-(4-氟苯基)丁-1,3-二炔基]苯
  参考文献：
  名称：

  Rh(I)-Catalyzed Decarbonylation of Diynones via C–C Activation: Orthogonal Synthesis of Conjugated Diynes

  摘要：

  Utilization of C-C bond activation as a unique mode of reactivity for constructing C-C bonds provides new strategies for preparing important organic molecules. Development of a Rh(I)-catalyzed C-C activation of diynones to synthesize symmetrical and unsymmetrical conjugated diynes through decarbonylation is reported. This C-C cleavage strategy takes advantage of the innate reactivity of conjugated ynones without relying on any ring strain or auxiliary directing group. This alkynation method also has orthogonal properties compared to typical cross-coupling reactions.

  DOI：

  10.1021/ol400815y
• 作为产物：
  描述：

  甲酸甲酯 、 1-(2,2-二溴乙烯基)-4-氟苯 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 2.25h， 以34%的产率得到1,5-bis(4-fluorophenyl)penta-1,4-diyn-3-ol
  参考文献：
  名称：

  Rh(I)-Catalyzed Decarbonylation of Diynones via C–C Activation: Orthogonal Synthesis of Conjugated Diynes

  摘要：

  Utilization of C-C bond activation as a unique mode of reactivity for constructing C-C bonds provides new strategies for preparing important organic molecules. Development of a Rh(I)-catalyzed C-C activation of diynones to synthesize symmetrical and unsymmetrical conjugated diynes through decarbonylation is reported. This C-C cleavage strategy takes advantage of the innate reactivity of conjugated ynones without relying on any ring strain or auxiliary directing group. This alkynation method also has orthogonal properties compared to typical cross-coupling reactions.

  DOI：

  10.1021/ol400815y

文献信息

• An Unexpected Domino Reaction of β-Keto Sulfones with Acetylene Ketones Promoted by Base: Facile Synthesis of 3(2<i>H</i> )-Furanones and Sulfonylbenzenes
  作者：Wei Tong、Qian-Yu Li、Yan-Li Xu、Heng-Shan Wang、Yan-Yan Chen、Ying-Ming Pan

  DOI：10.1002/adsc.201700830

  日期：2017.11.23

  An unexpected domino reaction of β‐keto sulfones with acetylene ketones has been developed. The domino reaction of β‐keto sulfones with diynones proceeded smoothly in the presence of 30 mol% K2CO3 without other additives, and afforded the novel 3(2H)‐furanone derivatives. On replacing the diynones with terminal alkyne ketones, the reaction regioselectivity was changed and sulfonylbenzenes were obtained

  β-酮砜与乙炔酮发生了意想不到的多米诺反应。在没有其他添加剂的情况下，在30 mol％K 2 CO 3的存在下，β-酮砜与二炔酮的多米诺反应顺利进行，得到了新颖的3（2 H）-呋喃酮衍生物。用末端炔烃酮取代二炔酮后，反应区域选择性改变，并通过苯环化获得磺酰苯，收率很高。
• Transition Metal-Free Synthesis of 3-Alkynylpyrrole-2-carboxylates<i>via</i>Michael Addition/Intramolecular Cyclodehydration
  作者：Qing-hu Teng、Yan-li Xu、Ying Liang、Heng-shan Wang、Ying-chun Wang、Ying-ming Pan

  DOI：10.1002/adsc.201501073

  日期：2016.6.16

  the synthesis of 3‐alkynylpyrrole‐2‐carboxylates from diynones and glycine esters or 2‐aminoacetophenone hydrochloride has been developed. This transformation provides a large range of substituted pyrroles in good to excellent yields with the elimination of water as the only by‐product. The detailed mechanistic studies elucidated that this transformation involves a Michael addition/intramolecular cyclodehydration

  已开发出一种无过渡金属的高效方法，该方法可从二炔酮和甘氨酸酯或2-氨基苯乙酮盐酸盐合成3-炔基吡咯-2-羧酸酯。这种转变提供了多种取代的吡咯，其收率高至优异，同时消除了水作为唯一的副产物。详细的机械研究表明，这种转变涉及迈克尔加成/分子内环脱水过程。
• Brønsted Acid Catalyzed and NIS-Promoted Cyclization of Diynones: Selective Synthesis of 4-Pyrone, 4-Pyridone, and 3-Pyrrolone Derivatives
  作者：Yi-Feng Qiu、Fang Yang、Zi-Hang Qiu、Mei-Jin Zhong、Li-Jing Wang、Yu-Ying Ye、Bo Song、Yong-Min Liang

  DOI：10.1021/jo402055a

  日期：2013.12.6

  Brønsted acid catalyzed tandem cyclization was found to be highly effective for the preparation of a series of polysubstituted 4-pyrones from diynones (yield up to 99%). 4-Pyridone and 3-pyrrolone derivatives were also selectively synthesized by employing NIS and/or Brønsted acid. NIS as an electrophilic reagent could promote these reactions efficiently and rapidly under very mild reaction conditions

  发现布朗斯台德酸催化的串联环化对于从二炔酮制备一系列多取代的4-吡喃酮非常有效（收率高达99％）。还通过使用NIS和/或布朗斯台德酸选择性地合成了4-吡啶酮和3-吡咯烷酮衍生物。NIS作为亲电子试剂可以在非常温和的反应条件下有效而迅速地促进这些反应。
• Synthesis of Highly Substituted 3-Formylfurans by a Gold(I)-Catalyzed Oxidation/1,2-Alkynyl Migration/Cyclization Cascade
  作者：Tao Wang、Shuai Shi、Max M. Hansmann、Eva Rettenmeier、Matthias Rudolph、A. Stephen K. Hashmi

  DOI：10.1002/anie.201310146

  日期：2014.4.1

  3‐Formylfuran derivatives are core structures of a variety of bioactive natural products. However, procedures for their preparation are still rare and generally inefficient in terms of atom economy: These methods require multiple steps or harsh reaction conditions and show selectivity problems. An efficient gold(I)‐catalyzed cascade reaction that leads to 3‐formylfurans from easily accessible starting

  3-甲酰呋喃衍生物是多种生物活性天然产物的核心结构。但是，制备它们的程序仍然很少见，并且就原子经济性而言通常是低效的：这些方法需要多个步骤或苛刻的反应条件，并显示出选择性问题。现在描述一种有效的金（I）催化的级联反应，该反应可从易于获取的起始原料生成3-甲酰呋喃。在N存在下，从相应的对称和不对称的1,4-二炔-3-醇中获得了多种3-甲酰基呋喃氧化效果好至极佳。同位素标记实验以及DFT计算都支持一种机制，在这种机制下，在最初的氧转移后，1,2-炔基迁移比氢化物转移更有利；随后进行环化以提供所需的官能化的呋喃核。
• Copper-Catalyzed Cascade Aminoalkynylation–Oxidation of Propargylic Alcohols: Stereospecific Synthesis of (<i>Z</i>)-2-Amino Conjugated Enynals/Enynones
  作者：Jiaqiong Sun、Guangfan Zheng、Yongmei Fu、Lihong Wang、Yan Li、Qian Zhang

  DOI：10.1021/acs.orglett.8b02272

  日期：2018.9.21

  Copper-catalyzed cascade aminoalkynylation–oxidation of propargylic alcohols has been realized, sterospecifically providing an array of (Z)-2-amino conjugated enynals/enynones in good yields under mild conditions. This transformation involves a rare 1,3-alkynyl migration of propargylic alcohols and simultaneously forms C–C, C–N, and C═O bonds. Furthermore, (Z)-2-amino conjugated enynals were applied

  铜催化的炔丙醇的级联氨基炔化反应已经实现，在温和条件下立体定向提供了良好收率的（Z）-2-氨基共轭烯醇/烯酮阵列。这种转化涉及稀有的炔丙基醇的1,3-炔基迁移，并同时形成C–C，C–N和C = O键。此外，（Z）-2-氨基共轭烯被应用于有效地合成3,5-二取代-1 H-吡咯-2-甲醛和共轭烯醇衍生物。