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IJMS
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Design and Application of Organic Superbases—from Theory to Experiment
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Design and Application of Organic Superbases—from Theory to Experiment

A special issue of International Journal of Molecular Sciences (ISSN 1422-0067). This special issue belongs to the section "Physical Chemistry and Chemical Physics".

Deadline for manuscript submissions: 20 May 2025 | Viewed by 4039

Special Issue Editor

Dr. Borislav Kovačević

E-Mail Website
Guest Editor
Group for Computational Life Sciences, Division of Physical Chemistry, Ruđer Bošković Institute, Bijenička Cesta 54, HR-10000 Zagreb, Croatia
Interests: molecular design; reaction mechanisms; organic catalysis; enzyme catalysis; structure-function relationship

Special Issue Information

Dear Colleagues,

The design and synthesis of nonionic, metal-free organic superbases have attracted significant attention over the past few decades. These investigations aim to discover new compounds with strong basic properties while also exploring their potential as catalysts in organic synthesis. Although numerous inorganic bases with high basicity can serve as base catalysts, the advantages of organic superbases, compared to their inorganic counterparts, are found in their solubility in organic reaction media, mild reaction conditions, and enhanced selectivity. The computational approach to designing superbases gained popularity with the development of computational methods capable of accurately predicting the thermodynamic basicity of molecules. Numerous structures with superbasic properties have been theoretically predicted. However, a significant portion of these structures remains challenging to synthesize experimentally. Additionally, while thermodynamic basicity is an important factor for the application of superbases, other factors such as kinetic basicity, thermodynamic stability, and molecular weight also play key roles. It is essential to consider all of these factors when proposing new superbases. The Special Issue of IJMS aims to gather original research papers that focus on both the computational design and experimental synthesis of new superbases, as well as review articles that present established concepts from a modern perspective. It serves as a platform for sharing diverse approaches to addressing the challenges encountered in this field.

Dr. Borislav Kovačević
Guest Editor

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Keywords

  • organic superbases
  • computational study
  • synthesis
  • structrue-function relationship
  • catalysis

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Published Papers (3 papers)

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Research

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15 pages, 2759 KiB  
Article
Strong Bases Design: Key Techniques and Stability Issues
by Andrey V. Kulsha, Oleg A. Ivashkevich, Dmitry A. Lyakhov and Dominik Michels
Int. J. Mol. Sci. 2024, 25(16), 8716; https://doi.org/10.3390/ijms25168716 - 9 Aug 2024
Viewed by 1011
Abstract
Theoretical design of molecular superbases has been attracting researchers for more than twenty years. General approaches were developed to make the bases potentially stronger, but less attention was paid to the stability of the predicted structures. Hence, only a small fraction of the [...] Read more.
Theoretical design of molecular superbases has been attracting researchers for more than twenty years. General approaches were developed to make the bases potentially stronger, but less attention was paid to the stability of the predicted structures. Hence, only a small fraction of the theoretical research has led to positive experimental results. Possible stability issues of extremely strong bases are extensively studied in this work using quantum chemical calculations on a high level of theory. Several step-by-step design examples are discussed in detail, and general recommendations are given to avoid the most common stability problems. New potentially stable structures are theoretically studied to demonstrate the future prospects of molecular superbases design. Full article
(This article belongs to the Special Issue Design and Application of Organic Superbases—from Theory to Experiment)
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15 pages, 4842 KiB  
Article
Cocatalytic Activity of the Furfuryl and Oxanorbornane-Substituted Guanidines in the Aldol Reaction Catalyzed by (S)-Proline
by Luka Barešić, Monika Marijanović, Irena Dokli, Davor Margetić and Zoran Glasovac
Int. J. Mol. Sci. 2024, 25(10), 5570; https://doi.org/10.3390/ijms25105570 - 20 May 2024
Viewed by 1185
Abstract
This work investigated the cocatalytic activity of recently prepared guanidinium salts containing an oxanorbornane subunit in an (S)-proline-catalyzed aldol reaction. The activity was interpreted by the diastereoselectivity of the reaction (anti/syn ratio) and for the most interesting polycyclic [...] Read more.
This work investigated the cocatalytic activity of recently prepared guanidinium salts containing an oxanorbornane subunit in an (S)-proline-catalyzed aldol reaction. The activity was interpreted by the diastereoselectivity of the reaction (anti/syn ratio) and for the most interesting polycyclic guanidinium salt, the enantioselectivity of the reaction was determined. The results indicated a negative impact on the oxanorbornane unit if present as the flexible substituent. For most of the tested aldehydes, the best cocatalysts provided enantioselectivities above 90% and above 95% at room temperature and 0 °C, respectively, culminating in >99.5% for 4–chloro– and 2–nitrobenzaldehyde as the substrate. The barriers for forming four possible enantiomers were calculated and the results for two anti–enantiomers are qualitatively consistent with the experiment. Obtained results suggest that the representatives of furfurylguanidinium and rigid polycyclic oxanorbornane-substituted guanidinium salts are good lead structures for developing new cocatalysts by tuning the chemical space around the guanidine moiety. Full article
(This article belongs to the Special Issue Design and Application of Organic Superbases—from Theory to Experiment)
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Review

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36 pages, 5138 KiB  
Review
Strong Bases and beyond: The Prominent Contribution of Neutral Push–Pull Organic Molecules towards Superbases in the Gas Phase
by Ewa Daniela Raczyńska, Jean-François Gal and Pierre-Charles Maria
Int. J. Mol. Sci. 2024, 25(11), 5591; https://doi.org/10.3390/ijms25115591 - 21 May 2024
Cited by 1 | Viewed by 1281
Abstract
In this review, the principles of gas-phase proton basicity measurements and theoretical calculations are recalled as a reminder of how the basicity PA/GB scale, based on Brønsted–Lowry theory, was constructed in the gas-phase (PA—proton affinity and/or GB—gas-phase basicity in the enthalpy and Gibbs [...] Read more.
In this review, the principles of gas-phase proton basicity measurements and theoretical calculations are recalled as a reminder of how the basicity PA/GB scale, based on Brønsted–Lowry theory, was constructed in the gas-phase (PA—proton affinity and/or GB—gas-phase basicity in the enthalpy and Gibbs energy scale, respectively). The origins of exceptionally strong gas-phase basicity of some organic nitrogen bases containing N-sp3 (amines), N-sp2 (imines, amidines, guanidines, polyguanides, phosphazenes), and N-sp (nitriles) are rationalized. In particular, the role of push–pull nitrogen bases in the development of the gas-phase basicity in the superbasicity region is emphasized. Some reasons for the difficulties in measurements for poly-functional nitrogen bases are highlighted. Various structural phenomena being in relation with gas-phase acid–base equilibria that should be considered in quantum-chemical calculations of PA/GB parameters are discussed. The preparation methods for strong organic push–pull bases containing a N-sp2 site of protonation are briefly reviewed. Finally, recent trends in research on neutral organic superbases, leaning toward catalytic and other remarkable applications, are underlined. Full article
(This article belongs to the Special Issue Design and Application of Organic Superbases—from Theory to Experiment)
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