Transesterification of Non‐Activated Esters Promoted by Small Molecules Mimicking the Active Site of Hydrolases

Garrido‐González, José J.; Sánchez‐Santos, Estela; Habib, Asmaa; Ferreras, Ángel V. Cuevas; Sanz, Francisca; Morán, Joaquı́n R.; Arriba, Ángel L. Fuentes de

doi:10.1002/anie.202206072

Cited by 3 publications

(1 citation statement)

References 36 publications

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“…H-bonding phenomena are widely observed in organocatalytic and biocatalytic systems (Fig. 5) (51)(52)(53)(54)(55)(56)(57). For example, simple amines (such as A3 and A4) in combination with phenol derivatives have been identified as potent organocatalysts in ring-opening polymerization of lactides, whereby the reactivity of the primary alcohol is enhanced by H-bonding interaction with the applied tertiary amine (57).…”

Section: Mechanistic Implicationsmentioning

confidence: 99%

Closed-loop recyclability of a biomass-derived epoxy-amine thermoset by methanolysis

Wu,

Hartmann,

Berne

et al. 2024

Science

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Epoxy resin thermosets (ERTs) are an important class of polymeric materials. However, owing to their highly cross-linked nature, they suffer from poor recyclability, which contributes to an unacceptable level of environmental pollution. There is a clear need for the design of inherently recyclable ERTs that are based on renewable resources. We present the synthesis and closed-loop recycling of a fully lignocellulose-derivable epoxy resin (DGF/MBCA), prepared from dimethyl ester of 2,5-furandicarboxylic acid (DMFD), 4,4′-methylenebis(cyclohexylamine) (MBCA), and glycidol, which displays excellent thermomechanical properties (a glass transition temperature of 170°C, and a storage modulus at 25°C of 1.2 gigapascals). Notably, the material undergoes methanolysis in the absence of any catalyst, regenerating 90% of the original DMFD. The diamine MBCA and glycidol can subsequently be reformed by acetolysis. Application and recycling of DGF/MBCA in glass and plant fiber composites are demonstrated.

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Section: Mechanistic Implicationsmentioning

confidence: 99%

Closed-loop recyclability of a biomass-derived epoxy-amine thermoset by methanolysis

Wu,

Hartmann,

Berne

et al. 2024

Science

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Transesterification of Non‐Activated Esters Promoted by Small Molecules Mimicking the Active Site of Hydrolases

et al. 2022

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The synthesis of small molecules able to mimic the active site of hydrolytic enzymes has been largely pursued in recent decades. The high reaction rates and specificity shown by natural hydrolases present an attractive target, and yet the preparation of suitable small-molecule mimics remains challenging, requiring activated substrates to achieve productive outcomes.Here we present small synthetic artificial enzymes which mimic the catalytic site and the oxyanion hole of chymotrypsin and N-terminal hydrolases and are able to perform, for the first time, the transesterification of a non-activated ester such as ethyl acetate with methanol under mild and neutral reaction conditions.

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Efficient Cleavage of pUC19 DNA by Tetraaminonaphthols

Kost,

Scheffer,

Kalden

et al. 2024

ChemistryOpen

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In an attempt to create models of phosphodiesterases, we previously investigated bis(guanidinium) naphthols. Such metal‐free anion receptors cleaved aryl phosphates and also plasmid DNA. Observed reaction rates, however, could not compete with those of highly reactive metal complexes. In the present study, we have replaced the guanidines by ethylene diamine side chains which accelerates the plasmid cleavage by compound 13 significantly (1 mM 13: t1/2=22 h). Further gains in reactivity are achieved by azo coupling of the naphthol unit. The electron accepting azo group decreases the pKa of the hydroxy group. It can also serve as a dye label and a handle for attaching DNA binding moieties. The resulting azo naphthol 17 not only nicks (1 mM 17: t1/2~1 h) but also linearizes pUC19 DNA. Although the high reactivity of 17 seems to result in part from aggregation, in the presence of EDTA azo naphthol 17 obeys first order kinetics (1 mM 17: t1/2=4.8 h), reacts four times faster than naphthol 13 and surpasses by far the former bis(guanidinium) naphthols 4 and 5.

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Transesterification of Non‐Activated Esters Promoted by Small Molecules Mimicking the Active Site of Hydrolases

Cited by 3 publications

References 36 publications

Closed-loop recyclability of a biomass-derived epoxy-amine thermoset by methanolysis

Closed-loop recyclability of a biomass-derived epoxy-amine thermoset by methanolysis

Transesterification of Non‐Activated Esters Promoted by Small Molecules Mimicking the Active Site of Hydrolases

Efficient Cleavage of pUC19 DNA by Tetraaminonaphthols

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