1,4-diphenylbut-3-yne-1,2-dione | 127388-13-0

• 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: 1,4-diphenylbut-3-yne-1,2-dione
• 英文别名: 1,4-diphenyl-3-butyne-1,2-dione
• CAS: 127388-13-0
• 化学式: C₁₆H₁₀O₂
• 分子量: 234.254
• InChiKey: OXYFBILTYRSFTD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,4-diphenylbut-3-yne-1,2-dione 在 sodium tetrahydroborate 、 三苯基膦氯金 、 双三氟甲烷磺酰亚胺银盐 作用下， 以 甲醇 、 甲苯 为溶剂， 反应 5.5h， 生成 2,5-二苯基呋喃
  参考文献：
  名称：

  Oxidative Coupling of Terminal Alkyne with α-Hydroxy Ketone: An Expedient Approach toward Ynediones

  摘要：

  An efficient and mild copper-catalyzed one-pot approach toward ynediones has been established. A variety of ynediones were constructed directly through oxidative coupling of alkyne with alpha-hydroxy ketone. Oxygen-oxidizing and neutral conditions in one-pot for a wide range of substrates including natural product derivatives make this transformation highly efficient and practical. On the basis of control experiments, in situ IR measurements, and isotopic labeling experiments, a plausible mechanism involving intermediate phenylglyoxal was drawn. Applications by synthesis of various heterocycles were also investigated.

  DOI：

  10.1021/ol502298a
• 作为产物：
  描述：

  (E)-1,4-Diphenylbut-1-en-3-yne 在 氢溴酸 作用下， 以 二甲基亚砜 为溶剂， 反应 10.0h， 以13%的产率得到1,4-diphenylbut-3-yne-1,2-dione
  参考文献：
  名称：

  Chemoselective Oxidation of Carbon-Carbon Double or Triple Bonds to 1,2-Diketones with DMSO-Based Reagents

  摘要：

  HBr/DMSO 选择性地将 (E)-1-(2-苯基乙烯)-4-(苯基乙炔基)苯 (1) 中的双键氧化为 1,2-二酮 2。然而，I2/DMSO 和 PdCl2/DMSO 仅氧化1 中的三键变为 1,2-二酮 3。使用基于 DMSO 的试剂氧化 (E)-1,4-二苯基-1-丁烯-3-炔 (6) 时显示出类似的化学选择性趋势。

  DOI：

  10.1055/s-1995-4094

文献信息

• Ti(O^<i>i</i>Pr)₄-Facilitated Formal Deoxygenative Annulation of Alkynyl 1,2-Diketones for the Synthesis of Highly Functionalized Furans
  作者：Shouang Lan、Rui Liu、Xiangwen Kong、Jinggong Liu、Benlong Luo、Shuang Yang、Xinqiang Fang

  DOI：10.1021/acs.orglett.1c00291

  日期：2021.2.19

  A unique deoxygenative cyclodimerization of alkynyl 1,2-diketones facilitated by Ti(OiPr)4 is achieved, affording a series of highly functionalized furan products. An unusual C–C bond and C═O bond cleavage of the substrates is observed, and Ti(OiPr)4 plays triplicate roles in the reaction. Furthermore, the products show uncommon fluorescent emission in the solid state, indicating the potential practical

  通过Ti（O i Pr）4促进了炔基1,2-二酮的独特脱氧环二聚作用，提供了一系列高度官能化的呋喃产品。观察到底物有异常的C–C键和C═O键断裂，并且Ti（O i Pr）4在反应中起三重作用。此外，产品在固态时显示出不常见的荧光发射，表明该工作的潜在实际应用。
• Visible light-induced aerobic oxidation of diarylalkynes to α-diketones catalyzed by copper-superoxo at room temperature
  作者：Vaibhav Pramod Charpe、Arunachalam Sagadevan、Kuo Chu Hwang

  DOI：10.1039/d0gc00975j

  日期：——

  the visible light induced simple copper(II) chloride catalyzed oxidation of diarylacetylenes to α-diketones by molecular oxygen at room temperature. The in situ generated copper(II)-superoxo complex is a light-absorbing species that oxidizes inert diarylacetylenes to α-diketones. In contrast to reported photochemical processes, the current oxidation protocol does not require any exogenous photocatalyst

  我们已经开发了在室温下可见光诱导的简单的铜（II）氯化铜催化分子氧将二芳基乙炔氧化为α-二酮的方法。该原位生成的铜（II）-superoxo配合物是一种吸光物质，可将惰性的二芳基乙炔氧化为α-二酮。与报道的光化学过程相反，当前的氧化方案不需要任何外源的光催化剂或自由基引发剂。绿色化学指标评估表明，当前氧化过程的E因子比报道的光化学过程的E因子高约2.3倍。当前反应在0-100的EcoScale上得分为63，表明合成过程适当。因此，整个氧化过程简单，对环境无害且在经济上可行。
• Catalytic Syntheses of N-Heterocyclic Ynones and Ynediones by In Situ Activation of Carboxylic Acids with Oxalyl Chloride
  作者：Christina Boersch、Eugen Merkul、Thomas J. J. Müller

  DOI：10.1002/anie.201103296

  日期：2011.10.24

  bottleneck: α‐Keto carboxylic acids and N‐heterocyclic carboxylic acids are activated in situ with oxalyl chloride then catalytically alkynylated to give ynediones and N‐heterocyclic ynones efficiently in a one‐pot fashion. 5‐Acylpyrazoles and 2‐phenylaminopyrimidines, potentially interesting for pharmaceutical applications, are readily synthesized in concise one‐pot, three‐component syntheses.

  突破瓶颈：使用草酰氯将α-酮基羧酸和N-杂环羧酸原位活化，然后进行催化炔基化反应，以单锅方式有效地产生乙炔和N-杂环炔酮。5-酰基吡唑和2-苯基氨基嘧啶可能在药物应用中很有趣，它们可以通过简单的一锅，三成分合成方法轻松合成。
• N-Heterocyclic Carbene-Catalyzed Umpolung of Alkynyl 1,2-Diketones
  作者：Xiangwen Kong、Guoxiang Zhang、Shuang Yang、Xiaozhi Liu、Xinqiang Fang

  DOI：10.1002/adsc.201700700

  日期：2017.8.17

  umpolung of alkynyl 1,2‐diketones via N‐heterocyclic carbene (NHC) catalysis was achieved for the first time, allowing the rapid access to a large variety of synthetically and pharmaceutically important α‐pyrones under very mild conditions. A completely new NHC‐catalyzed umpolung pattern involving an O‐acylated allenolate as the key intermediate was proposed. Moreover, an unprecedented reaction pathway

  首次通过N杂环卡宾（NHC）催化实现炔基1,2-二酮的酯化反应，从而可以在非常温和的条件下快速获得多种合成和药学上重要的α-吡喃酮。提出了一种全新的NHC催化的mpolung模式，其中包含O-酰化的烯丙基酯作为关键中间体。此外，据推测，以一系列的基团迁移和新的键形成为特征的空前反应路径证明了产物的形成。
• Ruthenium-Catalyzed Oxidation of Alkenes at Room Temperature: A Practical and Concise Approach to α-Diketones
  作者：Shulin Chen、Zhaojun Liu、Erbo Shi、Long Chen、Wei Wei、Hong Li、Yannan Cheng、Xiaobing Wan

  DOI：10.1021/ol200716d

  日期：2011.5.6

  The catalytic oxidation of alkenes to α-diketones is unprecedented. A new oxidation of alkenes, catalyzed by a ruthenium complex, which allows an efficient route to α-diketones using TBHP as an oxidant is described. This methodology is highly functional group tolerant, is practically convenient, requires no additional ligand, and operates under mild conditions with short reaction times. Based upon

  烯烃催化氧化为α-二酮是前所未有的。描述了一种新的由钌配合物催化的烯烃氧化，可使用TBHP作为氧化剂有效地合成α-二酮。该方法具有高度的官能团耐受性，实用方便，不需要额外的配体，并且可在温和条件下以较短的反应时间运行。基于实验观察，提出了一个合理的机制。