1,5-bis(4-chlorophenyl)penta-1,4-diyn-3-ol | 51118-08-2

• 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-chlorophenyl)penta-1,4-diyn-3-ol
• CAS: 51118-08-2
• 化学式: C₁₇H₁₀Cl₂O
• 分子量: 301.172
• InChiKey: ISWCZPNGYGGVCJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.76
• 重原子数：
  20.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  20.23
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  1,5-bis(4-chlorophenyl)penta-1,4-diyn-3-ol 在 二甲基二硫 、 溴 作用下， 以 二氯甲烷 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 12.0h， 以54%的产率得到(4-bromo-5-(4-chlorophenyl)thiophen-2-yl)(4-chlorophenyl)methanone
  参考文献：
  名称：

  Diorganyl Dichalcogenides-Promoted Nucleophilic Closure of 1,4-Diyn-3-ols: Synthesis of 2-Benzoyl Chalcogenophenes

  摘要：

  We report here the preparation of chalcogenophene derivatives via cyclization reactions of diynols promoted by diorganyl dichalcogenides and a halogen source. Different chalcogenophenes, such as 4-halo-selenophenes, 4-butylselenyl-selenophenes, halo-thiophenes, and 4-methylthio-thiophenes, were selectively prepared in good yields from the same starting materials. The results revealed that the halogen source had a significant effect on the proportion of 4-bromo-selenophenes and 4-butylselenyl-selenophenes. The best yields of 4-iodo-selenopheties were obtained with iodine as a halogen source) while the use of NBS gave exclusively the 4-butylselenyl-selenophenes. The experiments also revealed that the cyclization reaction to form 4-halo-thiophene derivatives can also be controlled changing the ratios of reagents. The 4-iodo-thiophenes were exclusively obtained by using dimethyl disulfide (2.0 equiv) and iodine (1.5 equiv), while the 4-bromo-thiophenes were obtained When the reaction was carried out with a 1.5 molar ratio of dimethyl disulfide and a halogen source. In addition, the reaction of diynols with an excess of dimethyl disulfide in the presence of NBS gave the 4-methylthio-thiophenes as sole products. We also studied the application of chalcogenophenes obtained as starting materials in the Suzuki, Sonogashira, and Ullmann cross-coupling reactions.

  DOI：

  10.1021/acs.joc.5b02334
• 作为产物：
  描述：

  甲酸甲酯 、 1-氯-4-(2,2-二溴乙烯基)苯 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 2.25h， 以49%的产率得到1,5-bis(4-chlorophenyl)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

• 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。
• Construction of 3-Sulfonyl Naphthalenes via Tandem Reaction of 1,4-Diyn-3-yl Esters with Sodium Sulfinates
  作者：Ziyi Guo、Yiming Zhao、Yu Wang、Meihua Xie、Jitan Zhang

  DOI：10.1021/acs.joc.1c00038

  日期：2021.5.7

  naphthalenes were constructed in good to high yields by AlCl3-mediated tandem reaction of 1,4-diyn-3-yl esters and sodium sulfinates. This reaction proceeded under mild reaction conditions and tolerated a variety of functional groups. Moreover, the mechanistic studies indicated that the initial formation of allene under DBU from 1,4-diyn-3-yl ester and a sequence of nucleophilic addition of sodium sulfinate,

  通过AlCl 3介导的1，4-二炔-3-基酯和亚磺酸钠的串联反应以良好至高收率构建了多取代的3-磺酰基萘。该反应在温和的反应条件下进行并且可以耐受多种官能团。此外，机理研究表明，在DBU下由1,4-二炔-3-基酯形成的异戊烯的初始形成和亚磺酸钠的亲核加成序列，异戊二烯的形成以及分子内环化可能涉及。
• Synthesis of Fully Substituted 3-Formyl-4-iodofurans<i>via</i>a Gold(I)-Catalyzed Oxidation/1,2-Alkynyl Migration/Cyclization/Iodination Cascade
  作者：Tao Wang、Shuai Shi、Matthias Rudolph、A. Stephen K. Hashmi

  DOI：10.1002/adsc.201400356

  日期：2014.7.7

  A highly efficient gold(I)‐catalyzed cascade reaction for the synthesis of fully substituted 3‐formyl‐4‐iodofurans has been developed. Mechanistic investigations indicate a reaction pathway that involves a direct iodination reaction of the organogold intermediate via functionalization of the AuC(sp2) bond, instead of a direct iodination of the 3‐formylfurans.

  已开发出一种高效的金（I）催化级联反应，用于合成完全取代的3-甲酰基-4-碘代呋喃。机械调查表明，涉及organogold中间的直接碘化反应的反应途径通过在Au的官能 C（SP 2）键，而不是3- formylfurans的直接碘化。