Pulsed electroconversion for highly selective enantiomer synthesis

Wattanakit, Chularat; Yutthalekha, Thittaya; Asssavapanumat, Sunpet; Lapeyre, Véronique; Kuhn, Alexander

doi:10.1038/s41467-017-02190-z

Cited by 52 publications

(55 citation statements)

References 59 publications

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“…To improve the performance of the imprinted mesoporous metal surfaces, pulsed electrosynthesis has been suggested . As mentioned above, in the case of the conventional steady‐state electroreduction of a prochiral compound, the interference of the reaction at the non‐imprinted external surface of metal results in a decrease in the global stereoselectivity.…”

Section: Properties and Applicationssupporting

confidence: 67%

“…Finally, the chirally imprinted cavities together with mesoporous channels are revealed after dissolution of the template molecules (Figure c) . This new concept has been successfully applied to various types of chirally imprinted cavities by using several chiral template molecules including 3,4‐dihydroxyphenylalanine (DOPA), mandelic acid (MA), phenyl ethanol (PE), and tryptophan enantiomers …”

Section: Synthesis Of Encoded Metal Structuresmentioning

confidence: 99%

“…To confirm the presence of imprinted chiral information, the Pt electrode initially imprinted with l ‐DOPA was scanned in the potential range −0.2 V to 1.25 V (vs. Ag/AgCl) in 0.5 m H 2 SO 4 , resulting in the complete destruction of the chiral information owing to an oxidation of the Pt surface atoms (Figure ) . This concept can be considered as a general approach, because it can be adapted to create various chiral cavities by using different templates …”

Section: Properties and Applicationsmentioning

confidence: 99%

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Encoding Chiral Molecular Information in Metal Structures

Wattanakit

Kuhn

2019

Chemistry A European J

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The concept of encoding molecular information in bulk metals has been proposed over the past decade. The structure of various types of molecules, including enantiomers, can be imprinted in achiral substrates. Typically, to encode metals with chiral information, several approaches, based on chemical and electrochemical concepts, can be used. In this Minireview, recent achievements with respect to the development of such materials are discussed, including the entrapment of chiral biomolecules in metals, the chiral imprinting of metals, as well as the combination of imprinting with nanostructuring. The features and potential applications of these designer materials, such as chirooptical properties, enantioselective adsorption and separation, as well as their use for asymmetric synthesis will be presented. This will illustrate that the development of molecularly encoded metal structures opens up very interesting perspectives, especially in the frame of chiral technologies.

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Section: Properties and Applicationssupporting

confidence: 67%

Section: Synthesis Of Encoded Metal Structuresmentioning

confidence: 99%

Section: Properties and Applicationsmentioning

confidence: 99%

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Encoding Chiral Molecular Information in Metal Structures

Wattanakit

Kuhn

2019

Chemistry A European J

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“…where transport and reaction control can be implemented to obtain complex functionality in polymers, control enantioselectivity in complex organic reactions, or enhance the production rate of oxidation products (38)(39)(40)(41)(42)(43)(44)(45)(46). More recently, pulsed electrosynthesis has been implemented in the electroreduction of CO 2 , where potential pulses have been shown to strongly influence the product distribution through a combination of electrode surface modifications, alteration of the intermediates' desorption energies, and control of reactant concentration in the EDL (47)(48)(49)(50).…”

Section: Significancementioning

confidence: 99%

Optimizing organic electrosynthesis through controlled voltage dosing and artificial intelligence

Blanco

Lee

Modestino

2019

Proc. Natl. Acad. Sci. U.S.A.

116

105

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Organic electrosynthesis can transform the chemical industry by introducing electricity-driven processes that are more energy efficient and that can be easily integrated with renewable energy sources. However, their deployment is severely hindered by the difficulties of controlling selectivity and achieving a large energy conversion efficiency at high current density due to the low solubility of organic reactants in practical electrolytes. This control can be improved by carefully balancing the mass transport processes and electrocatalytic reaction rates at the electrode diffusion layer through pulsed electrochemical methods. In this study, we explore these methods in the context of the electrosynthesis of adiponitrile (ADN), the largest organic electrochemical process in industry. Systematically exploring voltage pulses in the timescale between 5 and 150 ms led to a 20% increase in production of ADN and a 250% increase in relative selectivity with respect to the state-of-the-art constant voltage process. Moreover, combining this systematic experimental investigation with artificial intelligence (AI) tools allowed us to rapidly discover drastically improved electrosynthetic conditions, reaching improvements of 30 and 325% in ADN production rates and selectivity, respectively. This powerful AI-enhanced experimental approach represents a paradigm shift in the design of electrified chemical transformations, which can accelerate the deployment of more sustainable electrochemical manufacturing processes.

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“…In the case of the simultaneous presence of a target enantiomer, molecular cavities with chiral features can be generated in the mesopores . The developed materials have been used for applications ranging from chiral recognition and electroanalysis to asymmetric synthesis ,. Such chiral imprinted mesoporous metal surfaces (CIMMS) combine, synergistically, a very high active surface area and promising enantioselective recognition and synthesis abilities.…”

Section: Figurementioning

confidence: 99%

Potential‐Induced Fine‐Tuning of the Enantioaffinity of Chiral Metal Phases

et al. 2019

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Concepts leading to single enantiomers of chiral molecules are of crucial importance for many applications, including pharmacology and biotechnology. Recently, mesoporous metal phases encoded with chiral information have been developed. Fine‐tuning of the enantioaffinity of such structures by imposing an electric potential is proposed, which can influence the electrostatic interactions between the chiral metal and the target enantiomer. This allows the binding affinity between the chiral metal and the target enantiomer to be increased, and thus, the discrimination between two enantiomers to be improved. The concept is illustrated by generating chiral encoded metals in a microfluidic channel by reduction of a platinum salt in the presence of a liquid crystal and l‐tryptophan as a chiral model template. After removal of the template molecules, the modified microchannel retains a pronounced chiral character. The chiral recognition efficiency of the microchannel can be fine‐tuned by applying a suitable potential to the metal phase. This enables the separation of both components of a racemate flowing through the channel. The approach constitutes a promising and complementary strategy in the frame of chiral discrimination technologies.

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Pulsed electroconversion for highly selective enantiomer synthesis

Cited by 52 publications

References 59 publications

Encoding Chiral Molecular Information in Metal Structures

Encoding Chiral Molecular Information in Metal Structures

Optimizing organic electrosynthesis through controlled voltage dosing and artificial intelligence

Potential‐Induced Fine‐Tuning of the Enantioaffinity of Chiral Metal Phases

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