Sustainable chemo-enzymatic preparation of enantiopure (<i>R</i>)-β-hydroxy-1,2,3-triazoles <i>via</i> lactic acid bacteria-mediated bioreduction of aromatic ketones and a heterogeneous “click” cycloaddition reaction in deep eutectic solvents

Vitale, Paola; Lavolpe, Francesco; Valerio, Francesca; Biase, Mariaelena Di; Perna, Filippo Maria; Messina, Eugenia; Agrimi, Gennaro; Pisano, Isabella; Capriati, Vito

doi:10.1039/d0re00067a

Cited by 22 publications

(15 citation statements)

References 68 publications

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“…Since it was first introduced by Sharpless [19] and Meldal, [20] click chemistry has become a privileged reaction in the chemists′ toolbox [21] and it has shown numerous advantages including easy product recovery, inoffensive by‐product formation, modular reaction with wide scope and many inexpensive, readily available starting materials, catalyst, ligands, and so on [22] . Moreover, 1,2,3‐triazoles have found application to a wide variety of research areas, including organic and pharmaceutical chemistry, bioconjugation, drug discovery, polymer, nano‐ and material sciences [21–23] . CuAAc click reactions have been explored and analyzed in many different green solvents and reaction media, including DESs [24] .…”

Section: Introductionmentioning

confidence: 99%

Base‐Free Copper‐Catalyzed Azide‐Alkyne Click Cycloadditions (CuAAc) in Natural Deep Eutectic Solvents as Green and Catalytic Reaction Media**

et al. 2021

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The click cycloaddition of azides to alkynes affording 1,2,3‐triazoles is a widely used and effective chemical transformation, applied to obtain relevant products in medicine, biology, and materials science. In this work, a set of natural deep eutectic solvents (NADESs) has been investigated in the copper‐catalyzed azide‐alkyne cycloaddition reactions (CuAAc) as green and catalytic reaction media. The use of these innovative solvents has been shown to improve the reaction effectiveness, giving excellent yields. NADESs proved to be “active” in their reducing capabilities in several cases and for the absence of added bases in all the performed reactions: DFT calculations demonstrated in fact the involvement of H‐bonds between DESs and alkynes, as well as stabilization of copper catalytic intermediates. The green experimental conditions, the absence of a base, the low temperatures, the lowering of reagent amounts, and the possibility of recycling of the solvents, outline the great potential of NADESs for CuAAc.

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Section: Introductionmentioning

confidence: 99%

Base‐Free Copper‐Catalyzed Azide‐Alkyne Click Cycloadditions (CuAAc) in Natural Deep Eutectic Solvents as Green and Catalytic Reaction Media**

et al. 2021

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“…Optically active chiral alcohols play an essential role in medicinal chemistry (Brands et al 2003 ; Chen and de Souza 2019 ; Perrone et al 2008 ; Vitale et al 2020 ). ( R )-1-[3-(Trifluoromethyl)phenyl]ethanol (( R )-MTF-PEL) is a key chiral building block for the preparation of neuroprotective compounds like ( R )-3-(1-(3-(trifluoromethyl)phenyl)ethoxy)azetidine-1-carboxamide (Scheme 1 ) (Snape et al 2001 ).…”

Section: Introductionmentioning

confidence: 99%

Effective asymmetric preparation of (R)-1-[3-(trifluoromethyl)phenyl]ethanol with recombinant E. coli whole cells in an aqueous Tween-20/natural deep eutectic solvent solution

et al. 2021

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Abstract(R)-1-[3-(Trifluoromethyl)phenyl]ethanol ((R)-MTF-PEL) is an important chiral building block for the synthesis of a neuroprotective compound, (R)-3-(1-(3-(trifluoromethyl)phenyl)ethoxy)azetidine-1-carboxamide. In this work, an effective whole-cell-catalyzed biotransformation was developed to produce (R)-MTF-PEL, and its productivity was increased by medium engineering strategy. The recombinant E. coli BL21(DE3)-pET28a(+)-LXCAR-S154Y variant affording carbonyl reductase was adopted for the reduction of 3'-(trifluoromethyl)acetophenone to (R)-MTF-PEL with enantiomeric excess (ee) > 99.9%. The addition of 0.6% Tween-20 (w/v) boosted the bioreduction, because the substrate concentration was increased by 4.0-fold than that in the neat buffer solution. The biocatalytic efficiency was further enhanced by introducing choline chloride: lysine (ChCl:Lys, molar ratio of 1:1) in the reaction medium, because the product yield reached 91.5% under 200 mM substrate concentration in the established Tween-20/ChCl:Lys-containing system, which is the highest ever reported for (R)-MTF-PEL production. The optimal reduction conditions were as follows: 4% (w/v) ChCl:Lys, 12.6 g (DCW)/L recombinant E. coli cells, pH 7.0, 30 ℃ and 200 rpm, reaction for 18 h. The combined strategy of surfactant and NADES has great potential in the biocatalytic process and the synthesis of chiral alcohols.

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“…As part of our ongoing research in DES chemistry, we reported recently on the preparation of valuable heterocycles by (a) nucleophilic substitution (tetrahydrofuran derivatives) [4], (b) heterocyclodehydration reactions (2-aminoimidazoles, 2-pyrazinones, benzoxazines, thiophenes) [5][6][7][8], (c) carbon-sulfur bond-forming reactions [9], (d) directed ortho-metalation and nucleophilic acyl substitution strategies [10], (e) Pd-catalyzed aminocarbonylation of aryl iodides, Suzuki-Miyaura and Sonogashira cross-coupling reactions [11][12][13], (f) Cu-catalyzed C-N coupling reactions [14], and (g) heterogeneous "click" cycloaddition reactions [15] using DESs as environmentally responsible and non-innocent reaction media. Telescoped, one-pot transformations of phenacyl halides to symmetrical 2,5-disubstituted pyrazines (A), through phenacyl azides as intermediates, were also found to take place smoothly using such neoteric solvents (Scheme 1, path a) [16].…”

Section: Introductionmentioning

confidence: 99%

Regiodivergent synthesis of functionalized pyrimidines and imidazoles through phenacyl azides in deep eutectic solvents

Vitale

Cicco

Cellamare

et al. 2020

Beilstein J. Org. Chem.

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We report that phenacyl azides are key compounds for a regiodivergent synthesis of valuable, functionalized imidazole (32–98% yield) and pyrimidine derivatives (45–88% yield), with a broad substrate scope, when using deep eutectic solvents [choline chloride (ChCl)/glycerol (1:2 mol/mol) and ChCl/urea (1:2 mol/mol)] as environmentally benign and non-innocent reaction media, by modulating the temperature (25 or 80 °C) in the presence or absence of bases (Et3N).

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Sustainable chemo-enzymatic preparation of enantiopure (R)-β-hydroxy-1,2,3-triazoles via lactic acid bacteria-mediated bioreduction of aromatic ketones and a heterogeneous “click” cycloaddition reaction in deep eutectic solvents

Abstract: A chemo-enzymatic strategy for the preparation of enantiopure (R)-β-hydroxy-1,2,3-triazoles using a lactic acid bacterium as a whole-cell biocatalyst and a heterogeneous “click” cycloaddition reaction in deep eutectic solvents is disclosed.

Cited by 22 publications

References 68 publications

Base‐Free Copper‐Catalyzed Azide‐Alkyne Click Cycloadditions (CuAAc) in Natural Deep Eutectic Solvents as Green and Catalytic Reaction Media**

Base‐Free Copper‐Catalyzed Azide‐Alkyne Click Cycloadditions (CuAAc) in Natural Deep Eutectic Solvents as Green and Catalytic Reaction Media**

Effective asymmetric preparation of (R)-1-[3-(trifluoromethyl)phenyl]ethanol with recombinant E. coli whole cells in an aqueous Tween-20/natural deep eutectic solvent solution

Regiodivergent synthesis of functionalized pyrimidines and imidazoles through phenacyl azides in deep eutectic solvents

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