2-methyl-3-(naphthalen-2-ylthio)propanoic acid

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 2-methyl-3-(naphthalen-2-ylthio)propanoic acid
• 英文别名: 2-Methyl-3-naphthalen-2-ylsulfanylpropanoic acid
• 化学式: C₁₄H₁₄O₂S
• mdl: MFCD12430113
• 分子量: 246.33
• InChiKey: CNDOMYMQHSYYMK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.214
• 拓扑面积：
  62.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-methyl-3-(naphthalen-2-ylthio)propanoic acid 在 manganese(IV) oxide 、 草酰氯 、 hydrazine hydrate 、 sodium sulfate 、 N,N-二甲基甲酰胺 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 21.5h， 生成 tert-butyl 2''-methyl-2'',3''-dihydro-10H-dispiro[acridine-9,2'-thiirane-3',1''-benzo[f]thiochromene]-10-carboxylate
  参考文献：
  名称：

  An unexpected bidirectional molecular rotor from unidirectional molecular motor via a stereoselective enamine-imine tautomerization process

  摘要：

  Developing stereoselective synthetic method is very important to access chiral molecular devices. We herein demonstrate how a proton initiated stereoselective enamine-imine tautomerization converts a molecular motor into a simple rotor with high diastereoselectivity (>20:1 dr). NMR and X-ray crystallography were used to elucidate the structures of both the motor and rotor unambiguously. The activated motion of the rotor about its central single bond was studied from variable temperature NMR (293423 K) and DFT calculations provide evidence of the origin of diastereoselectivity of enamine-imine tautomerization as well as the rotor dynamics with barrier as high as 39.3 kcal/mol. Results from our work may benefit future design towards stereocontrolled and adaptive molecular machines. (C) 2020 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2020.152373
• 作为产物：
  描述：

  甲基丙烯酸 、 2-萘硫醇 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 以74 %的产率得到2-methyl-3-(naphthalen-2-ylthio)propanoic acid
  参考文献：
  名称：

  第二代分子马达 Pd 复合物中的耦合旋转和振荡运动

  摘要：

  分子机器为响应材料的开发提供了许多机会，并在分子系统中引入自主运动。虽然基本的分子开关和马达在受到外部刺激时会执行一种类型的运动，但开发能够执行耦合运动的分子系统对于开发更先进的分子机械至关重要。过度拥挤的基于烯烃的旋转分子马达是设计此类系统的理想基础，因为它们经历了由光引发的受控旋转，从而实现了出色的时空精度。在这里，我们展示了第二代旋转电机的 Pd 复合体示例，其 Pd 中心在电机旋转时相对于电机铁芯进行耦合振荡运动。我们通过 UV-vis、NMR 研究了这种现象，和密度泛函理论计算来支持我们的结论。通过这种由光驱动分子马达驱动的耦合旋转-振荡运动的演示，我们为开发在其操作中集成不同类型运动的更先进的分子机器提供了坚实的基础。

  DOI：

  10.1021/jacs.2c08267

文献信息

• Spectroscopic and Theoretical Identification of Two Thermal Isomerization Pathways for Bistable Chiral Overcrowded Alkenes
  作者：Jos C. M. Kistemaker、Stefano F. Pizzolato、Thomas van Leeuwen、Thomas C. Pijper、Ben L. Feringa

  DOI：10.1002/chem.201602276

  日期：2016.9.12

  higher temperatures for the thermal isomerization, namely a thermal E–Z isomerization (TEZI) and a thermal helix inversion (THI). These processes were also studied computationally whereby a new strategy was developed for calculating the TEZI barrier for second‐generation overcrowded alkenes. To demonstrate that these overcrowded alkenes can be employed as bistable switches, photochromic cycling was performed

  手性分子开关在响应材料和动态分子系统中发挥着重要作用。在这里，我们介绍了四种手性过度拥挤烯烃的合成及其光化学和热行为的实验和计算研究。通过紫外光照射，通过高产率的E - Z异构化生成具有相反螺旋度的亚稳态非对映异构体。使用 CD 光谱和 HPLC 分析对亚稳态1 – 4的动力学研究揭示了在较高温度下热异构化的两条途径，即热E – Z异构化（TEZI）和热螺旋反转（THI）。还对这些过程进行了计算研究，从而开发了一种新策略来计算第二代过度拥挤烯烃的 TEZI 势垒。为了证明这些过度拥挤的烯烃可以用作双稳态开关，进行了光致变色循环，这表明烯烃在多个辐照循环中表现出良好的选择性和抗疲劳性。特别是开关3在前后光开关中表现最好，而开关1在光生亚稳态形式的热稳定性方面表现出色。总体而言，所研究的烯烃显示出非凡且前所未有的开关特性组合，包括动态螺旋性、可逆性、选择性、抗疲劳性和热稳定性。
• Fluorine-Substituted Molecular Motors with a Quaternary Stereogenic Center
  作者：Peter Štacko、Jos C. M. Kistemaker、Ben L. Feringa

  DOI：10.1002/chem.201700581

  日期：2017.5.11

  A series of unprecedented second generation molecular motors featuring a quaternary stereogenic center substituted with a fluorine atom has been synthesized. It is demonstrated that a seemingly benign replacement of the stereogenic hydrogen for a fluorine atom, regarded as a common substituent in pharmacology, resulted in a dramatic change in the energetic profile of thermal helix inversion. The barrier

  已经合成了一系列前所未有的第二代分子马达，这些马达具有被氟原子取代的四级立体中心。已经证明，在药理学中被认为是常见的取代基的立体生成的氢被氟原子替代，看起来是良性的，导致了热螺旋转化的高能曲线发生了戏剧性的变化。发现热螺旋反转的势垒大大增加（增加了20-30 kJ mol -1），这可能是由于当氟原子被迫通过电机的下半部时，由于位阻增加而导致的过渡态不稳定。这导致热螺旋反转的激活势垒高于反向热E–Z的势垒。异构化，损害运动功能。当在设计阶段考虑到这些限制时，就可以成功地制备出能够进行单向旋转的氟代电动机。
• Fredga, Arkiv foer Kemi, 1952, vol. 3, p. 123,126
  作者：Fredga

  DOI：——

  日期：——
• Construction of Photo‐Responsive Pd ₂ L ₄ ‐Type Nanocages based on Feringa's Second‐Generation Motor and Its Guest Binding Ability for C ₆₀
  作者：Yunan Qin、Jingpeng Xiong、Quan Li、Yuexing Zhang、Ming‐Hua Zeng

  DOI：10.1002/chem.202201821

  日期：2022.10.21

  AbstractWe present the construction of a M2L4‐type metal‐organic nanocage featuring four endohedral Feringa's motor motifs and its adaptive encapsulation towards a C60 guest molecule. The structure of the cage, though complicated on the 1H NMR spectrum due to the adoption of mixed ligands, was unambiguously characterized with a combination of ESI‐MS, 2D DOSY, 13C NMR and particularly the SAXS technique. The molecular motor within the cage demonstrated similar photophysical properties to the uncoordinated one, indicating the motor's function was not compromised when it was anchored in such a confined nanospace. Furthermore, the nanocage showed good guest encapsulation ability towards C60, and a guest induced‐fit behavior of the cage was revealed based on the extensive SAXS analysis and molecular dynamics simulation. The adaptive motorized nanocage reported here represents one of the very few examples of integrating individual motors into a discrete nanoconfined system and offers prospects to achieve its non‐equilibrium functions.
• An unexpected bidirectional molecular rotor from unidirectional molecular motor via a stereoselective enamine-imine tautomerization process
  作者：Jingpeng Xiong、Quan Li、Ming-Hua Zeng

  DOI：10.1016/j.tetlet.2020.152373

  日期：2020.10

  Developing stereoselective synthetic method is very important to access chiral molecular devices. We herein demonstrate how a proton initiated stereoselective enamine-imine tautomerization converts a molecular motor into a simple rotor with high diastereoselectivity (>20:1 dr). NMR and X-ray crystallography were used to elucidate the structures of both the motor and rotor unambiguously. The activated motion of the rotor about its central single bond was studied from variable temperature NMR (293423 K) and DFT calculations provide evidence of the origin of diastereoselectivity of enamine-imine tautomerization as well as the rotor dynamics with barrier as high as 39.3 kcal/mol. Results from our work may benefit future design towards stereocontrolled and adaptive molecular machines. (C) 2020 Elsevier Ltd. All rights reserved.