4-[(4-Fluorophenyl)methoxy]but-2-yn-1-ol | 1011470-67-9

• 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: 4-[(4-Fluorophenyl)methoxy]but-2-yn-1-ol
• CAS: 1011470-67-9
• 化学式: C₁₁H₁₁FO₂
• 分子量: 194.206
• InChiKey: FIYJHVOBNBEWDL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-[(4-Fluorophenyl)methoxy]but-2-yn-1-ol 在 1,5,7-三氮杂双环[4.4.0]癸-5-烯 、 silver(I) acetate 、 2-二环己膦基-2'-(N,N-二甲胺)-联苯 、 苯酚 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 30.0 ℃ 、2.0 MPa 条件下， 反应 2.0h， 生成
  参考文献：
  名称：

  An Organocatalytic Route to endo‐Vinylene Carbonates from Carbon Dioxide‐Based exo‐Vinylene Carbonates

  摘要：

  摘要 开发了一种将外乙烯基碳酸酯（exo-VCs）异构化为内乙烯基碳酸酯（endo-VCs）的有机催化路线。外乙烯基碳酸酯起始原料可以很容易地从丙炔醇中通过与二氧化碳的环化反应获得。本研究表明，在 N-杂环碱和苯酚存在下，这些外-VC 会异构化成热力学上更稳定的内-VC。为了阐明其机理，我们进行了密度泛函理论（DFT）研究，以解决电荷分离步骤描述方面的难题。在温和的反应条件下，这一异构化过程产生了多种多样的内 VCs，产率和化学选择性都非常好。

  DOI：

  10.1002/adsc.202301374
• 作为产物：
  描述：

  丁炔二醇 、 4-氟溴苄 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 14.0h， 以28%的产率得到4-[(4-Fluorophenyl)methoxy]but-2-yn-1-ol
  参考文献：
  名称：

  Malaria-Infected Mice Are Cured by Oral Administration of New Artemisinin Derivatives

  摘要：

  In four or five chemical steps from the 1,2,4-trioxane artemisinin, a new series of 23 trioxane dimers has been prepared. Eleven of these new trioxane dimers cure malaria-infected mice via oral dosing at 3 x 30 mg/kg. The clinically used trioxane drug sodium artesunate prolonged mouse average survival to 7.2 days with this oral dose regimen. In comparison, animals receiving no drug die typically on day 6-7 postinfection. At only 3 x 10 mg/kg oral dosing, seven dimers prolong the lifetime of malaria-infected mice to days 14-17, more than double the chemotherapeutic effect of sodium artesunate. Ten new trioxane dimers at only a single oral dose of 30 mg/kg prolong mouse average survival to days 8.7-13.7, and this effect is comparable to that of the fully synthetic trioxolane drug development candidate OZ277, which is in phase 11 clinical trials.

  DOI：

  10.1021/jm701168h

文献信息

• Expanded Ring NHC Silver Carboxylate Complexes as Efficient and Reusable Catalysts for the Carboxylative Cyclization of Unsubstituted Propargylic Derivatives
  作者：Alejandro Cervantes‐Reyes、Tobias Saxl、Philipp M. Stein、Matthias Rudolph、Frank Rominger、Abdullah M. Asiri、A. Stephen K. Hashmi

  DOI：10.1002/cssc.202002822

  日期：2021.6.8

  α-methylene cyclic carbonates. Derived from X-ray diffraction studies, the molecular geometry and the concept of buried volume were employed to describe the structural and steric features of these silver complexes. Their stability and efficiency as catalysts have been demonstrated by the synthesis of 29 carboxylation products (72–98 % yield) at low catalyst loadings (0.01–1.5 mol%). Characteristics are high

  由庞大的 N-杂环卡宾 [ BP DPr, 1,3-双(2,6-二异丙基苯基)-1,3-diazonine-2-ylidene] 配体稳定，新的BP DPrAgO 2形式的羧酸银配合物CR (R=Me, Ph) 已在溶液和固态中合成并完全表征，并在具有挑战性的二氧化碳固定中用作唯一催化剂（碱、添加剂，在某些情况下，无溶剂）用于合成恶唑烷酮和α-亚甲基环状碳酸酯的未取代炔丙基衍生物。根据 X 射线衍射研究，分子几何形状和埋藏体积的概念被用来描述这些银配合物的结构和空间特征。它们作为催化剂的稳定性和效率已通过在低催化剂负载量（0.01-1.5 mol%）下合成 29 种羧化产物（72-98% 产率）得到证明。特点是周转数高（高达 9400）、催化剂可回收性（第 7 次循环后产率高达 96%，银络合物不分解），
• Malaria-Infected Mice Are Cured by Oral Administration of New Artemisinin Derivatives
  作者：Gary H. Posner、Wonsuk Chang、Lindsey Hess、Lauren Woodard、Sandra Sinishtaj、Aimee R. Usera、William Maio、Andrew S. Rosenthal、Alvin S. Kalinda、John G. D’Angelo、Kimberly S. Petersen、Remo Stohler、Jacques Chollet、Josefina Santo-Tomas、Christopher Snyder、Matthias Rottmann、Sergio Wittlin、Reto Brun、Theresa A. Shapiro

  DOI：10.1021/jm701168h

  日期：2008.2.1

  In four or five chemical steps from the 1,2,4-trioxane artemisinin, a new series of 23 trioxane dimers has been prepared. Eleven of these new trioxane dimers cure malaria-infected mice via oral dosing at 3 x 30 mg/kg. The clinically used trioxane drug sodium artesunate prolonged mouse average survival to 7.2 days with this oral dose regimen. In comparison, animals receiving no drug die typically on day 6-7 postinfection. At only 3 x 10 mg/kg oral dosing, seven dimers prolong the lifetime of malaria-infected mice to days 14-17, more than double the chemotherapeutic effect of sodium artesunate. Ten new trioxane dimers at only a single oral dose of 30 mg/kg prolong mouse average survival to days 8.7-13.7, and this effect is comparable to that of the fully synthetic trioxolane drug development candidate OZ277, which is in phase 11 clinical trials.
• An Organocatalytic Route to <i>endo</i>‐Vinylene Carbonates from Carbon Dioxide‐Based <i>exo</i>‐Vinylene Carbonates
  作者：Chang Qiao、Philipp D. Engel、Levi A. Ziegenhagen、Frank Rominger、Ansgar Schäfer、Peter Deglmann、Peter Rudolf、Peter Comba、A. Stephen K. Hashmi、Thomas Schaub

  DOI：10.1002/adsc.202301374

  日期：2024.1.30

  An organocatalytic route has been developed for the isomerization of exo‐vinylene carbonates (exo‐VCs) to endo‐vinylene carbonates (endo‐VCs). The exo‐VC starting material can easily be obtained from propargylic alcohols via cyclization with carbon dioxide. In this study, these exo‐VCs are shown to isomerize to the thermodynamically more stable endo‐VCs in the presence of an N‐heterocyclic base and phenol. Density functional theory (DFT) studies were conducted to elucidate the mechanism, tackling difficulties of the description of charge separation steps. This isomerization process delivers an ample diversity of endo‐VCs in good to excellent yields and chemoselectivities under mild reaction conditions.

  摘要 开发了一种将外乙烯基碳酸酯（exo-VCs）异构化为内乙烯基碳酸酯（endo-VCs）的有机催化路线。外乙烯基碳酸酯起始原料可以很容易地从丙炔醇中通过与二氧化碳的环化反应获得。本研究表明，在 N-杂环碱和苯酚存在下，这些外-VC 会异构化成热力学上更稳定的内-VC。为了阐明其机理，我们进行了密度泛函理论（DFT）研究，以解决电荷分离步骤描述方面的难题。在温和的反应条件下，这一异构化过程产生了多种多样的内 VCs，产率和化学选择性都非常好。