Effects of solvents on the DACBO-catalyzed vinylogous Henry reaction of isatin with 3,5-dimethyl-4-nitroisoxazole “on-water” and in solution from QM/MM MC simulations

Yang, Lijun; Zhao, Jianming; Yang, Xin; Chen, Ming; Yang, Xue

doi:10.1039/c9ra00082h

Cited by 7 publications

(4 citation statements)

References 53 publications

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“…Quantum mechanics/molecular mechanics (QM/MM) approaches are often used to understand catalyst-free Type III reactions, and a few examples of organocatalytic reactions have been reported. 56 The difficulty of calculating catalytic reactions lies in the fact that the structural fluctuation of a catalyst and its surroundings in aqueous environments, because of hydration, significantly multiplies the number of transition states en route to the desired product. Although the artificial force-induced reaction (AFIR) method enabled the challenging systematic sampling of transition states to determine the stereochemical information on the reactions performed in aqueous media, 57 there has been no QM study on catalytically accelerated Type III reactions at the interface.…”

Section: New Frontiers and Challenges In Synthetic Organic “Aquachemistry”mentioning

confidence: 99%

Synthetic Organic “Aquachemistry” that Relies on Neither Cosolvents nor Surfactants

Kitanosono

Kobayashi

2021

ACS Cent. Sci.

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There is a growing awareness of the underlying power of catalytic reactions in water that is not limited to innate sustainability alone. Some Type III reactions are catalytically accelerated without dissolution of reactants and are occasionally highly selective, as shown by comparison with the corresponding reactions run in organic solvents or under solvent-free conditions. Such catalysts are highly diversified, including hydrophilic, lipophilic, and even solid catalysts. In this Outlook, we highlight the impressive characteristics of illustrative catalysis that is exerted despite the immiscibility of the substrates and reveal the intrinsic benefits of these enigmatic reactions for synthetic organic chemistry, albeit with many details remaining unclear. We hope that this brief introduction to the expanding field of synthetic organic “aquachemistry” will inspire organic chemists to use the platform to invent new transformations.

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Section: New Frontiers and Challenges In Synthetic Organic “Aquachemistry”mentioning

confidence: 99%

Synthetic Organic “Aquachemistry” that Relies on Neither Cosolvents nor Surfactants

Kitanosono

Kobayashi

2021

ACS Cent. Sci.

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“…Zhang et al first reported the vinylogous, henry reaction between isatin and 3,5-dialkyl-4-nitroisoxazole, leading to isoxazolesubstituted 3-hydroxy-2-oxindole derivatives, medicinally important compounds [20], also provided the basis for removal of industrial dye wastewater [21]. In this study, we discuss with detail "Synthesis of isatin and its derivatives and their applications in biological system" because isatin play a key effects like ascorbic acid, hydroxyl amino acids, omeprazole, thiol compounds and imidazole etc.…”

Section: -P-(p-(alkoxycarbonyl) Phenyl) Carbamoyl) Phenyl)mentioning

confidence: 99%

Synthesis of Isatin and Its Derivatives and their Applications in Biological System

Aziz

Ullah²,

Ullah³

et al. 2020

BJSTR

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Here investigations were made to study the variant developments in the synthesis of isatin and its derivatives. This review comprehended the various synthetic methods especially, sandmeyer synthesis, stolle synthesis and gassman synthesis for the synthesis of isatin. The isatin and its derivatives played a key role in biomedical applications. The isatin and its derivatives are used as bactericide, fungicide, anti-HIV, anti-epileptic, anti-instigative and so on. The isatin derivatives are helpful in inhibiting the activity of the urease and α-glucosidase enzymes and reduce the risks of pyelonephritis, gastric problems and diabetes. This review highlighted the synthetic routes for the synthesis of isatin and the beneficial aspects of isatin and its derivatives in biomedical field.

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“…A lot of effort has been undertaken to computationally describe and understand the selectivity of organic reactions. Reactions already studied in literature include the Wittig reaction [ 35 ], organocatalytic addition to

-unsaturated ketones [ 36 ], chiral catalyzed ketimine-ene reactions [ 37 ], weak acid dissociation [ 38 ], organocatalytic S

2 reactions [ 39 , 40 ], the catalytic vinylogous Henry reaction [ 41 ], base-catalyzed Knoevenagel condensations [ 42 , 43 ], the Meyer–Schuster rearrangement [ 44 ], enantiomerization of axially chiral biphenyls [ 45 ], and also proline-catalyzed reactions [ 46 , 47 , 48 ]. While some of these studies obtained their results by using static quantum chemical calculations and frequently described solvent influence via continuum solvation models [ 37 , 39 , 40 , 42 , 43 , 44 , 49 , 50 , 51 ], others were based on molecular dynamics simulations and often used tools such as metadynamics [ 35 , 38 , 43 , 46 , 52 , 53 , 54 ] and umbrella sampling [ 45 ] to investigate the potential energy surfaces of the reactions.…”

Section: Introductionmentioning

confidence: 99%

Exploring Free Energy Profiles of Enantioselective Organocatalytic Aldol Reactions under Full Solvent Influence

Weiß

Brehm

2020

Molecules

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We present a computational study on the enantioselectivity of organocatalytic proline-catalyzed aldol reactions between aldehydes in dimethylformamide (DMF). To explore the free energy surface of the reaction, we apply two-dimensional metadynamics on top of ab initio molecular dynamics (AIMD) simulations with explicit solvent description on the DFT level of theory. We avoid unwanted side reactions by utilizing our newly developed hybrid AIMD (HyAIMD) simulation scheme, which adds a simple force field to the AIMD simulation to prevent unwanted bond breaking and formation. Our condensed phase simulation results are able to nicely reproduce the experimental findings, including the main stereoisomer that is formed, and give a correct qualitative prediction of the change in syn:anti product ratio with different substituents. Furthermore, we give a microscopic explanation for the selectivity. We show that both the explicit description of the solvent and the inclusion of entropic effects are vital to a good outcome—metadynamics simulations in vacuum and static nudged elastic band (NEB) calculations yield significantly worse predictions when compared to the experiment. The approach described here can be applied to a plethora of other enantioselective or organocatalytic reactions, enabling us to tune the catalyst or determine the solvent with the highest stereoselectivity.

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Effects of solvents on the DACBO-catalyzed vinylogous Henry reaction of isatin with 3,5-dimethyl-4-nitroisoxazole “on-water” and in solution from QM/MM MC simulations

Abstract: QM/MM MC simulations indicate that the special hydrogen bonding effects are the main source of the rate enhancement of the title reaction on water.

Cited by 7 publications

References 53 publications

Synthetic Organic “Aquachemistry” that Relies on Neither Cosolvents nor Surfactants

Synthetic Organic “Aquachemistry” that Relies on Neither Cosolvents nor Surfactants

Synthesis of Isatin and Its Derivatives and their Applications in Biological System

Exploring Free Energy Profiles of Enantioselective Organocatalytic Aldol Reactions under Full Solvent Influence

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