Source of Rate Acceleration for Carbocation Cyclization in Biomimetic Supramolecular Cages

Nguyen, Quynh Nhu; Xia, Kay T.; Zhang, Yue; Chen, Nanhao; Morimoto, Mariko; Pei, Xiaokun; Ha, Yang; Guo, Jinghua; Yang, Wanli; Wang, Lee‐Ping; Bergman, Robert G.; Raymond, Kenneth N.; Toste, F. Dean; Tantillo, Dean J.

doi:10.1021/jacs.2c04179

Cited by 27 publications

(19 citation statements)

References 66 publications

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“…Overall, computational results are in excellent agreement with experiment and provide a deeper understanding of the process identifying the key aspects of catalysis. While this manuscript was under review appeared a publication by Tantillo, Toste, Bergman, Raymond and coworkers on the same topic reaching essentially the same conclusions about the origin of catalysis [45] …”

Section: Introductionmentioning

confidence: 72%

“…We thank D. Tantillo and coworkers for generously sharing results before publication (their work appeared in Ref. [45]). The authors acknowledge the financial support of the Spanish MINECO-FEDER (Grants PID2020-116861GBÀ I00 and RED2018-102387-T).…”

Section: Acknowledgementsmentioning

confidence: 99%

“…While this manuscript was under review appeared a publication by Tantillo, Toste, Bergman, Raymond and coworkers on the same topic reaching essentially the same conclusions about the origin of catalysis. [45] …”

Section: Introductionmentioning

confidence: 99%

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Catalysis by [Ga₄L₆]¹²⁻ Metallocage on the Nazarov Cyclization: The Basicity of Complexed Alcohol is Key

Norjmaa

Himo

Maréchal

et al. 2022

Chemistry A European J

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The Nazarov cyclization is investigated in solution and within K12[Ga4L6] supramolecular organometallic cage by means of computational methods. The reaction needs acidic condition in solution but works at neutral pH in the presence of the metallocage. The reaction steps for the process are analogous in both media: (a) protonation of the alcohol group, (b) water loss and (c) cyclization. The relative Gibbs energies of all the steps are affected by changing the environment from solvent to the metallocage. The first step in the mechanism, the alcohol protonation, turns out to be the most critical one for the acceleration of the reaction inside the metallocage. In order to calculate the relative stability of protonated alcohol inside the cavity, we propose a computational scheme for the calculation of basicity for species inside cavities and can be of general use. These results are in excellent agreement with the experiments, identifying key steps of catalysis and providing an in‐depth understanding of the impact of the metallocage on all the reaction steps.

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Section: Introductionmentioning

confidence: 72%

Section: Acknowledgementsmentioning

confidence: 99%

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Catalysis by [Ga₄L₆]¹²⁻ Metallocage on the Nazarov Cyclization: The Basicity of Complexed Alcohol is Key

Norjmaa

Himo

Maréchal

et al. 2022

Chemistry A European J

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“…Supramolecular architectures based on coordination complexes have been extensively explored and have been demonstrated to display excellent properties for biomimetic catalysis. − A coordination complex is build up from a metal ion and ligands (Figure ). Depending on the type of metal, its oxidation state, and the structure of the ligands, specific structures can be made via self-assembly .…”

Section: General Principlesmentioning

confidence: 99%

Supramolecular Coordination Cages for Artificial Photosynthesis and Synthetic Photocatalysis

et al. 2023

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Because sunlight is the most abundant energy source on earth, it has huge potential for practical applications ranging from sustainable energy supply to light driven chemistry. From a chemical perspective, excited states generated by light make thermodynamically uphill reactions possible, which forms the basis for energy storage into fuels. In addition, with light, open-shell species can be generated which open up new reaction pathways in organic synthesis. Crucial are photosensitizers, which absorb light and transfer energy to substrates by various mechanisms, processes that highly depend on the distance between the molecules involved. Supramolecular coordination cages are well studied and synthetically accessible reaction vessels with single cavities for guest binding, ensuring close proximity of different components. Due to high modularity of their size, shape, and the nature of metal centers and ligands, cages are ideal platforms to exploit preorganization in photocatalysis. Herein we focus on the application of supramolecular cages for photocatalysis in artificial photosynthesis and in organic photo(redox) catalysis. Finally, a brief overview of immobilization strategies for supramolecular cages provides tools for implementing cages into devices. This review provides inspiration for future design of photocatalytic supramolecular host−guest systems and their application in producing solar fuels and complex organic molecules.

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“…The 3D molecular structures were prepared to implement in the optimization calculations to reach the minimized energy structures. Then, the thermochemical frequency calculations were performed on the already optimized molecules to evaluate the values of enthalpy (H) for each of the investigated models (22).…”

Section: Computational Molecular Modelingmentioning

confidence: 99%

Sb(V) Kaempferol and Quercetin Derivative Complexes: Synthesis, Characterization and Antileishmanial Activities

et al. 2022

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Background: Recent studies on Leishmaniasis treatment have confirmed the antiparasitic effects of flavonols and organic antimony pentavalent [(Sb(V)] complexes. Objectives: This study aimed to identify new Sb(V) complexes by combining the benefits of antimonials and flavonols as well as by optimizing their properties. Methods: Kaempferol and quercetin peracetate were prepared using acetic anhydride in pyridine. By performing regioselective synthesis, 7-O-paramethylbenzyl as an electron-donating group and 7-O-paranitrobenzyl as an electron-withdrawing group were added to quercetin, and, then, the synthesis of Sb(V) kaempferol and quercetin derivative complexes were performed using SbCl5 solution in glacial acetic acid. The structures were confirmed by UV, ESI mass, IR, 1H-, and 13C-NMR spectral data, and the Stoichiometry of the ligand-metal complex by the mole ratio method. Computational molecular modeling was conducted using the Gaussian program. Results: The structures were confirmed based on the results from UV, nuclear magnetic resonance (NMR), and electrospray ionization (ESI) mass analyses (3-12). Among the produced compounds, 11 and 12 as newly described, and other compounds as pre-defined compounds were identified. According to the results from biological test, kaempferol triacetate with more lipophilicity showed the highest anti-promastigote activity with an IC50 value of 14.93 ± 2.21 µM. As for anti-amastigote activity, despite the differences, all antimony complexes showed anti-amastigote effects in vitro with IC50 values of 0.52 to 14.50 µM. Conclusions: All flavonol Sb(V) complexes showed higher activity compared to meglumine antimonate in anti-amastigote effect. Inside the host macrophages, by breaking down the complex into antimony and quercetin or kaempferol analogs, the observed antiparasitic effects may have been related to both Sb(V)/Sb(III) conversion and flavonoid antileishmanial activities.

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Source of Rate Acceleration for Carbocation Cyclization in Biomimetic Supramolecular Cages

Cited by 27 publications

References 66 publications

Catalysis by [Ga₄L₆]¹²⁻ Metallocage on the Nazarov Cyclization: The Basicity of Complexed Alcohol is Key

Catalysis by [Ga₄L₆]¹²⁻ Metallocage on the Nazarov Cyclization: The Basicity of Complexed Alcohol is Key

Supramolecular Coordination Cages for Artificial Photosynthesis and Synthetic Photocatalysis

Sb(V) Kaempferol and Quercetin Derivative Complexes: Synthesis, Characterization and Antileishmanial Activities

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Source of Rate Acceleration for Carbocation Cyclization in Biomimetic Supramolecular Cages

Cited by 27 publications

References 66 publications

Catalysis by [Ga4L6]12− Metallocage on the Nazarov Cyclization: The Basicity of Complexed Alcohol is Key

Catalysis by [Ga4L6]12− Metallocage on the Nazarov Cyclization: The Basicity of Complexed Alcohol is Key

Supramolecular Coordination Cages for Artificial Photosynthesis and Synthetic Photocatalysis

Sb(V) Kaempferol and Quercetin Derivative Complexes: Synthesis, Characterization and Antileishmanial Activities

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Catalysis by [Ga₄L₆]¹²⁻ Metallocage on the Nazarov Cyclization: The Basicity of Complexed Alcohol is Key

Catalysis by [Ga₄L₆]¹²⁻ Metallocage on the Nazarov Cyclization: The Basicity of Complexed Alcohol is Key